Dynamically vulcanized polyarylene sulfide composition

ABSTRACT

Polyarylene sulfide compositions are described that exhibit high strength and flexibility. Methods for forming the polyarylene sulfide compositions are also described. Formation methods include dynamic vulcanization of a polyarylene sulfide composition that includes an impact modifier dispersed throughout the polyarylene sulfide. A crosslinking agent is combined with the other components of the composition following dispersal of the impact modifier throughout the composition. The crosslinking agent reacts with the impact modifier to form crosslinks within and among the polymer chains of the impact modifier. The compositions can exhibit excellent physical characteristics at extreme temperatures and can be used to form, e.g., tubular member such as pipes and hoses and fibers.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.13/804,675 having a filing date of Mar. 14, 2013, which claims filingbenefit of U.S. Provisional Patent application 61/623,618 having afiling date of Apr. 13, 2012; U.S. Provisional Patent application61/665,423 having a filing date of Jun. 28, 2012; U.S. ProvisionalPatent application 61/678,370 having a filing date of Aug. 1, 2012; U.S.Provisional Patent application 61/703,331 having a filing date of Sep.20, 2012; U.S. Provisional Patent application 61/707,314 having a filingdate of Sep. 28, 2012; U.S. Provisional Patent application 61/717,899having a filing date of Oct. 24, 2012; and U.S. Provisional Patentapplication 61/739,926 having a filing date of Dec. 20, 2012; all ofwhich are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

Polymer blends that exhibit flexibility in addition to high strength andresistance properties are of significant commercial interest. Suchblends have been formed in the past by uniformly mixing an elasticcomponent with a thermoplastic polyolefin such that the elastomer isintimately and uniformly dispersed as a discrete or co-continuous phasewithin a continuous phase of the polyolefin. Vulcanization of thecomposite crosslinks the components and provides improved temperatureand chemical resistance to the composition. When vulcanization iscarried out during combination of the various polymeric components it istermed dynamic vulcanization.

Polyarylene sulfides are high-performance polymers that may withstandhigh thermal, chemical, and mechanical stresses and are beneficiallyutilized in a wide variety of applications. Polyarylene sulfides haveoften been blended with other polymers to improve characteristics of theproduct composition. For example, elastomeric impact modifiers have beenfound beneficial for improvement of the physical properties of apolyarylene sulfide composition. Compositions including blends ofpolyarylene sulfides with impact modifying polymers have been consideredfor high performance, high temperature applications.

Unfortunately, elastomeric polymers generally considered useful forimpact modification are not compatible with polyarylene sulfides andphase separation has been a problem in forming compositions of the two.Attempts have been made to improve the composition formation, forinstance through the utilization of compatibilizers. However, even uponsuch modifications, compositions including polyarylene sulfides incombination with impact modifying polymers still fail to provide productperformance as desired, particularly in applications that require bothhigh heat resistance and high impact resistance.

What are needed in the art are polyarylene sulfide compositions thatexhibit high strength characteristics as well as resistance todegradation, even in extreme temperature environments, while maintainingdesirable processing characteristics.

SUMMARY OF THE INVENTION

Disclosed in one embodiment is a polyarylene sulfide composition thatincludes a polyarylene sulfide and a crosslinked impact modifier. Thepolyarylene sulfide composition exhibits high toughness and goodflexibility. For instance, the polyarylene sulfide composition canexhibit a notched Charpy impact strength of greater than about 3 kJ/m²as measured according to ISO Test No. 179-1 at a temperature of 23° C.and a notched Charpy impact strength of greater than about 8 kJ/m² asmeasured according to ISO Test No. 179-1 at a temperature of −30° C.

Also disclosed is a method for forming a polyarylene sulfidecomposition. A method can include feeding polyarylene sulfide, an impactmodifier, and a cross linking agent to a melt processing unit. Morespecifically, the cross linking agent can be fed to the processing unitfollowing combination of the impact modifier and the polyarylene sulfideand following distribution of the impact modifier throughout thepolyarylene sulfide.

Also disclosed are products that can beneficially incorporate thepolyarylene sulfide composition including, without limitation, fibersand fibrous products and tubular members, including both single layerand multi-layer tubular members. Tubular members can encompass pipes andhoses suitable for carrying water, oil, gas, fuel, etc., for instance asmay be utilized in an automotive system. Other products as mayincorporate the polyarylene sulfide composition include sheathed cablesand wires and a variety of electrical components. Products can beparticularly well suited for use in extreme temperatures and/or inapplications in which temperatures may vary over a wide margin.

BRIEF DESCRIPTION OF THE FIGURES

The present disclosure may be better understood with reference to thefollowing figures:

FIG. 1 is a schematic representation of a process for forming thepolyarylene sulfide composition as disclosed herein.

FIG. 2 is a single layer tubular member as may be formed from thepolyarylene sulfide composition.

FIG. 3 illustrates a blow molding process as may be used in forming acomponent that includes the polyarylene sulfide composition.

FIG. 4 illustrates a continuous blow molding process as may be used informing a component that includes the polyarylene sulfide composition.

FIG. 5 is a multi-layer tubular member, one or more layers of which maybe formed from the polyarylene sulfide composition.

FIG. 6 illustrates an oil and gas system including a flexible riserflowline extending from the sea floor to a surface unit.

FIG. 7 illustrates an oil and gas production field incorporatingmultiple different types of flowlines that can include a polyarylenesulfide composition as described herein.

FIG. 8 is a schematic representation of a multilayer riser including abarrier layer formed of the polyarylene sulfide composition as describedherein.

FIG. 9 illustrates a bundled riser including multiple flowlines asdescribed herein.

FIG. 10A is a side view and FIG. 10B is a cross-sectional view of apipe-in-pipe flowline as may include one or more layers formed of thepolyarylene sulfide composition.

FIG. 11 illustrates a drawn fiber formation method as may be used informing fibers of the polyarylene sulfide composition.

FIG. 12 illustrates a formation method for forming melt-blown fibers ofthe polyarylene sulfide composition.

FIG. 13 illustrates a fibrous mat as may incorporate polyarylene sulfidefibers as described herein.

FIG. 14 illustrates a sheathed wire (FIG. 14A) and a sheathed cable(FIG. 14B) as may include the polyarylene sulfide composition.

FIG. 15 illustrates a cable harness as may include the polyarylenesulfide composition.

FIG. 16A and FIG. 16B illustrate a urea tank for a heavy duty truck asmay incorporate components including the polyarylene sulfidecomposition.

FIG. 17 illustrates another embodiment of a urea tank for a heavy dutytruck as may incorporate components including the polyarylene sulfidecomposition.

FIG. 18 illustrates a portion of a fuel system that can incorporate oneor more fuel lines as may be formed from a polyarylene sulfidecomposition as described herein.

FIG. 19 is a schematic illustration of an airplane fuselage as mayincorporate the polyarylene sulfide composition as described herein.

FIG. 20 illustrates the sample used in determination of melt strengthand melt elongation of polyarylene sulfide compositions describedherein.

FIG. 21 illustrates the effect of temperature change on the notchedCharpy impact strength of a polyarylene sulfide composition as describedherein and that of a comparison composition.

FIG. 22 is a scanning electron microscope image of a polyarylene sulfidecomposition as described herein (FIG. 22B) and a comparison polyarylenesulfide (FIG. 22A).

FIG. 23 compares the effect of sulfuric acid exposure on strengthcharacteristics of polyarylene sulfide compositions as described hereinand a comparison composition.

FIG. 24 provides the log of the complex viscosity obtained forpolyarylene sulfide compositions described herein as a function of theshear rate.

FIG. 25 provides the melt strength of polyarylene sulfide compositionsdescribed herein as a function of the Hencky strain.

FIG. 26 provides the melt elongation for polyarylene sulfidecompositions described herein as a function of Hencky strain.

FIG. 27 illustrates a blow molded container formed of the polyarylenesulfide composition.

FIG. 28A and FIG. 28B are cross sectional images of the container shownin FIG. 27.

FIG. 29 illustrates the daily weight loss for testing samples indetermination of permeation resistance of polyarylene sulfidecompositions to CE10 fuel blend.

FIG. 30 illustrates the daily weight loss for testing samples indetermination of permeation resistance of polyarylene sulfidecompositions to CM15A fuel blend.

FIG. 31 illustrates the daily weight loss for testing samples indetermination of permeation resistance of polyarylene sulfidecompositions to methanol.

DETAILED DESCRIPTION

It is to be understood by one of ordinary skill in the art that thepresent discussion is a description of exemplary embodiments only, andis not intended as limiting the broader aspects of the presentdisclosure.

The present disclosure is generally directed to polyarylene sulfidecompositions that exhibit excellent strength and flexibilitycharacteristics as well as resistance to chemical degradation due tocontact with, e.g., water, oils, gas, synthetic or natural chemicals,etc. Beneficially, the polyarylene sulfide composition can maintain goodphysical characteristics even when utilized in extreme temperatureapplications such as high temperatures as may be encountered inautomotive applications and low temperatures as may be encountered inpiping applications. The polyarylene sulfide can also maintain goodphysical characteristics under conditions in which the materials aresubjected to extreme temperature fluctuations.

The polyarylene sulfide compositions can be formed according to a meltprocessing technique that includes combining a polyarylene sulfide withan impact modifier to form a mixture and subjecting the mixture todynamic vulcanization. More specifically, the polyarylene sulfide can becombined with the impact modifier and this mixture can be subjected toshear conditions such that the impact modifier becomes well distributedthroughout the polyarylene sulfide. Following formation of the mixture,a polyfunctional crosslinking agent can be added. The polyfunctionalcrosslinking agent can react with the components of the mixture to formcrosslinks in the composition, for instance within and between thepolymer chains of the impact modifier.

Without being bound to any particular theory, it is believed that byadding the polyfunctional crosslinking agent to the polyarylene sulfidecomposition following distribution of the impact modifier throughout thepolyarylene sulfide, interaction between the polyarylene sulfide, theimpact modifier, and the crosslinking agent within the melt processingunit can be improved, leading to improved distribution of thecrosslinked impact modifier throughout the composition. The improveddistribution of the crosslinked impact modifier throughout thecomposition can improve the strength and flexibility characteristics ofthe composition, e.g., the ability of the composition to maintainstrength under deformation, as well as provide a composition with goodprocessibility that can be utilized to form a product that can exhibitexcellent resistance to degradation under a variety of conditions.

According to one embodiment, a formation process can includefunctionalization of the polyarylene sulfide. This embodiment canprovide additional sites for bonding between the impact modifier and thepolyarylene sulfide, which can further improve distribution of theimpact modifier throughout the polyarylene sulfide and further preventphase separation. Moreover, functionalization of the polyarylene sulfidecan include scission of the polyarylene sulfide chain, which candecrease the melt viscosity of the composition and improveprocessibility. This can also provide a polyarylene sulfide compositionthat is a low halogen, e.g., low chlorine composition that exhibitsexcellent physical characteristics and high resistance to degradation.

To provide further improvements to the polyarylene sulfide composition,the composition can be formed to include other conventional additivessuch as fillers, lubricants, colorants, etc. according to standardpractice.

The high strength and flexibility characteristics of the polyarylenesulfide composition can be evident by examination of the tensile,flexural, and/or impact properties of the materials. For example, thepolyarylene sulfide composition can have a notched Charpy impactstrength of greater than about 3 kJ/m², greater than about 3.5 kJ/m²,greater than about 5 kJ/m², greater than about 10 kJ/m², greater thanabout 15 kJ/m², greater than about 30 kJ/m², greater than about 33kJ/m², greater than about 40 kJ/m², greater than about 45 kJ/m², orgreater than about 50 kJ/m² as determined according to ISO Test No.179-1 (technically equivalent to ASTM D256, Method B) at 23° C. Theunnotched Charpy samples do not break under testing conditions of ISOTest No. 180 at 23° C. (technically equivalent to ASTM D256).

Beneficially, the polyarylene sulfide composition can maintain goodphysical characteristics even at extreme temperatures, including bothhigh and low temperatures. For instance, the polyarylene sulfidecomposition can have a notched Charpy impact strength of greater thanabout 8 kJ/m², greater than about 9 kJ/m², greater than about 10 kJ/m²,greater than about 14 kJ/m², greater than about 15 kJ/m², greater thanabout 18 kJ/m², or greater than about 20 kJ/m² as determined accordingto ISO Test No. 179-1 at −30° C.; and can have a notched Charpy impactstrength of greater than about 8 kJ/m², greater than about 9 kJ/m²,greater than about 10 kJ/m², greater than about 11 kJ/m², greater thanabout 12 kJ/m², or greater than about 15 kJ/m² as determined accordingto ISO Test No. 179-1 at −40° C.

Moreover, the effect of temperature change on the polyarylene sulfidecomposition can be surprisingly small. For instance, the ratio of thenotched Charpy impact strength as determined according to ISO Test No.179-1 at 23° C. to that at −30° C. can be greater than about 3.5,greater than about 3.6, or greater than about 3.7. Thus, and asdescribed in more detail in the example section below, as thetemperature increases the impact strength of the polyarylene sulfidecomposition also increases, as expected, but the rate of increase of theimpact strength is very high, particularly as compared to a compositionthat does not include the dynamically crosslinked impact modifier.Accordingly, the polyarylene sulfide composition can exhibit excellentstrength characteristics at a wide range of temperatures.

The polyarylene sulfide composition can exhibit very good tensilecharacteristics. For example, the polyarylene sulfide composition canhave a tensile elongation at yield of greater than about 4.5%, greaterthan about 6%, greater than about 7%, greater than about 10%, greaterthan about 25%, greater than about 35%, greater than about 50%, greaterthan about 70%, greater than about 75%, greater than about 80%, orgreater than about 90%. Similarly, the tensile elongation at break canbe quite high, for instance greater than about 10%, greater than about25%, greater than about 35%, greater than about 50%, greater than about70%, greater than about 75%, greater than about 80%, or greater thanabout 90%. The strain at break can be greater than about 5%, greaterthan about 15%, greater than about 20%, or greater than about 25%. Forinstance the strain at break can be about 90%. The yield strain canlikewise be high, for instance greater than about 5%, greater than about15%, greater than about 20%, or greater than about 25%. The yield stresscan be, for example, greater than about 50% or greater than about 53%.The polyarylene sulfide composition may have a tensile strength at breakof greater than about 30 MPa, greater than about 35 MPa, greater thanabout 40 MPa, greater than about 45 MPa, or greater than about 70 MPa.

In addition, the polyarylene sulfide composition can have a relativelylow tensile modulus. For instance, the polyarylene sulfide compositioncan have a tensile modulus less than about 3000 MPa, less than about2300 MPa, less than about 2000 MPa, less than about 1500 MPa, or lessthan about 1100 MPa as determined according to ISO Test No. 527 at atemperature of 23° C. and a test speed of 5 mm/min.

The polyarylene sulfide composition can exhibit good characteristicsafter annealing as well. For instance, following annealing at atemperature of about 230° C. for a period of time of about 2 hours, thetensile modulus of the composition can be less than about 2500 MPa, lessthan about 2300 MPa, or less than about 2250 MPa. The tensile strengthat break after annealing can be greater than about 50 MPa, or greaterthan about 55 MPa, as measured according to ISO Test No. 527 at atemperature of 23° C. and a test speed of 5 mm/min.

The polyarylene sulfide composition can also be utilized continuously athigh temperature, for instance at a continuous use temperature of up toabout 150° C., about 160° C., or about 165° C. without loss of tensilestrength. For example, the polyarylene sulfide composition can maintaingreater than about 95%, for instance about 100% of the original tensilestrength after 1000 hours of heat aging at 135° C. and can maintaingreater than about 95%, for instance about 100% of the original tensileelongation at yield after 1000 hours heat aging at 135° C.

Tensile characteristics can be determined according to ISO Test No. 527at a temperature of 23° C. and a test speed of 5 mm/min or 50 mm/min(technically equivalent to ASTM D623 at 23° C.).

The flexural characteristics of the composition can be determinedaccording to ISO Test No. 178 (technically equivalent to ASTM D790 at atemperature of 23° C. and a testing speed of 2 mm/min. For example, theflexural modulus of the composition can be less than about 2500 MPa,less than about 2300 MPa, less than about 2000 MPa, less than about 1800MPa, or less than about 1500 MPa. The polyarylene sulfide compositionmay have a flexural strength at break of greater than about 30 MPa,greater than about 35 MPa, greater than about 40 MPa, greater than about45 MPa, or greater than about 70 MPa.

The deflection temperature under load of the polyarylene sulfidecomposition can be relatively high. For example, the deflectiontemperature under load of the polyarylene sulfide composition can begreater than about 80° C., greater than about 90° C., greater than about100° C., or greater than about 105° C., as determined according to ISOTest No. 75-2 (technically equivalent to ASTM D790) at 1.8 MPa.

The Vicat softening point can be greater than about 200° C. or greaterthan about 250° C., for instance about 270° C. as determined accordingto the Vicat A test when a load of 10 N is used at a heating rate of 50K/hr. For the Vicat B test, when a load of 50 N is used at a heatingrate of 50 K/hr, the Vicat softening point can be greater than about100° C., greater than about 150° C. greater than about 175° C., orgreater than about 190° C., for instance about 200° C. The Vicatsoftening point can be determined according to ISO Test No. 306(technically equivalent to ASTM D1525).

The polyarylene sulfide composition can also exhibit excellent stabilityduring long term exposure to harsh environmental conditions. Forinstance, under long term exposure to an acidic environment, thepolyarylene sulfide composition can exhibit little loss in strengthcharacteristics. For instance, following 500 hours exposure to a strongacid (e.g., a solution of about 5% or more strong acid such as sulfuricacid, hydrochloric acid, nitric acid, perchloric acid, etc.), thepolyarylene sulfide composition can exhibit a loss in Charpy notchedimpact strength of less than about 17%, or less than about 16% followingexposure of about 500 hours to a strong acid solution at a temperatureof about 40° C., and can exhibit a loss in Charpy notched impactstrength of less than about 25%, or less than about 22% followingexposure of about 500 hours to a strong acid solution at a temperatureof about 80° C. Even under harsher conditions, for instance in a 10%sulfuric acid solution held at a temperature of about 80° C. for 1000hours, the polyarylene sulfide composition can maintain about 80% ormore of the initial Charpy notched impact strength. The polyarylenesulfide composition can also maintain desirable strength characteristicsfollowing exposure to other potentially degrading materials, such assalts, e.g., road salts as may be encountered in automotiveapplications.

Permeation resistance can be important for a wide variety ofapplications for the polyarylene sulfide composition, for instance whenutilizing the composition in formation of fuel lines, storage tanks, orthe like. The polyarylene sulfide composition can exhibit excellentpermeation resistance to a wide variety of materials. For instance, ashaped product formed of the polyarylene sulfide composition can exhibita permeation resistance to a fuel or a fuel source (e.g., gasoline,diesel fuel, jet fuel, unrefined or refined oil, etc.) of less thanabout 10 g-mm/m²-day, less than about 5 g-mm/m²-day, less than about 3g-mm/m²-day, or less than about 2 g-mm/m²-day. By way of example, thepolyarylene sulfide composition (or a product formed of the polyarylenesulfide composition) can exhibit a permeation resistance to an ethanolblend of ethanol/iso-octane/toluene at a weight ratio of 10:45:45 at 40°C. of less than about 10 g-mm/m²-day, less than about 3 g-mm/m²-day,less than about 2.5 g-mm/m²-day, less than about 1 g-mm/m²-day, or lessthan about 0.1 g-mm/m²-day. The permeation resistance to a blend of 15wt. % methanol and 85 wt. % oxygenated fuel (CM15A) at 40° C. can beless than about 5 g-mm/m²-day, less than about 3 g-mm/m²-day, less thanabout 2.5 g-mm/m²-day, less than about 1 g-mm/m²-day, less than about0.5 g-mm/m²-day, less than about 0.3 g-mm/m²-day, or less than about0.15 g-mm/m²-day. The permeation resistance to methanol at 40° C. can beless than about 1 g-mm/m²-day, less than about 0.5 g-mm/m²-day, lessthan about 0.25 g-mm/m²-day, less than about 0.1 g-mm/m²-day, or lessthan about 0.06 g-mm/m²-day. Permeation resistance can be determinedaccording to SAE Testing Method No. J2665. In addition, the polyarylenesulfide composition can maintain original density following long termexposure to hydrocarbons. For example, the composition can maintaingreater than about 95% of original density, greater than about 96% oforiginal density, such as about 99% of original density following longterm (e.g., greater than about 14 days) exposure to hydrocarbons such asheptane, cyclohexane, toluene, and so forth, or combinations ofhydrocarbons.

The polyarylene sulfide composition can also be resistant to uptake ofmaterials, and specifically hydrocarbons. For example, a moldedstructure formed of the composition can exhibit a volume change of lessthan about 25%, less than about 20%, or less than about 14% followingexposure to the hydrocarbon at a temperature of 130° C. for a period oftime of about two weeks.

The polyarylene sulfide composition can exhibit good heat resistance andflame retardant characteristics. For instance, the composition can meetthe V-0 flammability standard at a thickness of 0.2 millimeters Theflame retarding efficacy may be determined according to the UL 94Vertical Burn Test procedure of the “Test for Flammability of PlasticMaterials for Parts in Devices and Appliances”, 5th Edition, Oct. 29,1996. The ratings according to the UL 94 test are listed in thefollowing table:

Rating Afterflame Time (s) Burning Drips Burn to Clamp V-0 <10 No No V-1<30 No No V-2 <30 Yes No Fail <30 Yes Fail >30 No

The “afterflame time” is an average value determined by dividing thetotal afterflame time (an aggregate value of all samples tested) by thenumber of samples. The total afterflame time is the sum of the time (inseconds) that all the samples remained ignited after two separateapplications of a flame as described in the UL-94 VTM test. Shorter timeperiods indicate better flame resistance, i.e., the flame went outfaster. For a V-0 rating, the total afterflame time for five (5)samples, each having two applications of flame, must not exceed 50seconds. Using the flame retardant of the present invention, articlesmay achieve at least a V-1 rating, and typically a V-0 rating, forspecimens having a thickness of 0.2 millimeters.

The polyarylene sulfide composition can also exhibit good processingcharacteristics, for instance as demonstrated by the melt viscosity ofthe composition. For instance, the polyarylene sulfide composition canhave a melt viscosity of less than about 2800 poise as measured on acapillary rheometer at 316° C. and 400 sec⁻¹ with the viscositymeasurement taken after five minutes of constant shear. Moreover, thepolyarylene sulfide composition can exhibit improved melt stability overtime as compared to polyarylene sulfide compositions that do not includecrosslinked impact modifiers. Polyarylene sulfide compositions that donot include a crosslinked impact modifier tend to exhibit an increase inmelt viscosity over time, and in contrast, disclosed compositions canmaintain or even decrease in melt viscosity over time.

The polyarylene sulfide composition can have a complex viscosity asdetermined at low shear (0.1 radians per second (rad/s)) and 310° C. ofgreater than about 10 kPa/sec, greater than about 25 kPa/sec, greaterthan about 40 kPa/sec, greater than about 50 kPa/sec, greater than about75 kPa/sec, greater than about 200 kPa/sec, greater than about 250kPa/sec, greater than about 300 kPa/sec, greater than about 350 kPa/sec,greater than about 400 kPa/sec, or greater than about 450 kPa/sec.Higher value for complex viscosity at low shear is indicative of thecrosslinked structure of the composition and the higher melt strength ofthe polyarylene sulfide composition. In addition, the polyarylenesulfide composition can exhibit high shear sensitivity, which indicatesexcellent characteristics for use in formation processes such as blowmolding and extrusion processing.

FIG. 1 illustrates a schematic of a process that can be used in formingthe polyarylene sulfide composition. As illustrated, the components ofthe polyarylene sulfide composition may be melt-kneaded in a meltprocessing unit such as an extruder 100. Extruder 100 can be anyextruder as is known in the art including, without limitation, a single,twin, or multi-screw extruder, a co-rotating or counter rotatingextruder, an intermeshing or non-intermeshing extruder, and so forth. Inone embodiment, the composition may be melt processed in an extruder 100that includes multiple zones or barrels. In the illustrated embodiment,extruder 100 includes 10 barrels numbered 21-30 along the length of theextruder 100, as shown. Each barrel 21-30 can include feed lines 14, 16,vents 12, temperature controls, etc. that can be independently operated.A general purpose screw design can be used to melt process thepolyarylene composition. By way of example, a polyarylene sulfidecomposition may be melt mixed using a twin screw extruder such as aCoperion co-rotating fully intermeshing twin screw extruder.

In forming a polyarylene sulfide composition, the polyarylene sulfidecan be fed to the extruder 100 at a main feed throat 14. For instance,the polyarylene sulfide may be fed to the main feed throat 14 at thefirst barrel 21 by means of a metering feeder. The polyarylene sulfidecan be melted and mixed with the other components of the composition asit progresses through the extruder 100. The impact modifier can be addedto the composition in conjunction with the polyarylene sulfidecomposition at the main feed throat 14 or downstream of the main feedthroat, as desired.

At a point downstream of the main feed throat 14, and following additionof the impact modifier to the composition, the crosslinking agent can beadded to the composition. For instance, in the illustrated embodiment, asecond feed line 16 at barrel 26 can be utilized for addition of thecrosslinking agent. The point of addition for the crosslinking agent isnot particularly limited. However, the crosslinking agent can be addedto the composition at a point after the polyarylene sulfide has beenmixed with the impact modifier under shear such that the impact modifieris well distributed throughout the polyarylene sulfide.

The polyarylene sulfide may be a polyarylene thioether containing repeatunits of the formula (I):—[(Ar¹)_(n)-X]_(m)—[(Ar²)_(i)—Y]_(j)—[(Ar³)_(k)—Z]_(l)—[(Ar⁴)_(o)—W]_(p)—  (I)wherein Ar¹, Ar², Ar³, and Ar⁴ are the same or different and are aryleneunits of 6 to 18 carbon atoms; W, X, Y, and Z are the same or differentand are bivalent linking groups selected from —SO₂—, —S—, —SO—, —CO—,—O—, —COO— or alkylene or alkylidene groups of 1 to 6 carbon atoms andwherein at least one of the linking groups is —S—; and n, m, i, j, k, l,o, and p are independently zero or 1, 2, 3, or 4, subject to the provisothat their sum total is not less than 2. The arylene units Ar¹, Ar²,Ar³, and Ar⁴ may be selectively substituted or unsubstituted.Advantageous arylene systems are phenylene, biphenylene, naphthylene,anthracene and phenanthrene. The polyarylene sulfide typically includesmore than about 30 mol %, more than about 50 mol %, or more than about70 mol % arylene sulfide (—S—) units. In one embodiment the polyarylenesulfide includes at least 85 mol % sulfide linkages attached directly totwo aromatic rings.

In one embodiment, the polyarylene sulfide is a polyphenylene sulfide,defined herein as containing the phenylene sulfide structure—(C₆H₄—S)_(n)— (wherein n is an integer of 1 or more) as a componentthereof.

The polyarylene sulfide may be synthesized prior to forming thepolyarylene sulfide composition, though this is not a requirement of aprocess. Synthesis techniques that may be used in making a polyarylenesulfide are generally known in the art. By way of example, a process forproducing a polyarylene sulfide can include reacting a material thatprovides a hydrosulfide ion, e.g., an alkali metal sulfide, with adihaloaromatic compound in an organic amide solvent.

The alkali metal sulfide can be, for example, lithium sulfide, sodiumsulfide, potassium sulfide, rubidium sulfide, cesium sulfide or amixture thereof. When the alkali metal sulfide is a hydrate or anaqueous mixture, the alkali metal sulfide can be processed according toa dehydrating operation in advance of the polymerization reaction. Analkali metal sulfide can also be generated in situ. In addition, a smallamount of an alkali metal hydroxide can be included in the reaction toremove or react impurities (e.g., to change such impurities to harmlessmaterials) such as an alkali metal polysulfide or an alkali metalthiosulfate, which may be present in a very small amount with the alkalimetal sulfide.

The dihaloaromatic compound can be, without limitation, ano-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene,dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoicacid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenylsulfoxide or dihalodiphenyl ketone. Dihaloaromatic compounds may be usedeither singly or in any combination thereof. Specific exemplarydihaloaromatic compounds can include, without limitation,p-dichlorobenzene; m-dichlorobenzene; o-dichlorobenzene;2,5-dichlorotoluene; 1,4-dibromobenzene; 1,4-dichloronaphthalene;1-methoxy-2,5-dichlorobenzene; 4,4′-dichlorobiphenyl;3,5-dichlorobenzoic acid; 4,4′-dichlorodiphenyl ether;4,4′-dichlorodiphenylsulfone; 4,4′-dichlorodiphenylsulfoxide; and4,4′-dichlorodiphenyl ketone.

The halogen atom can be fluorine, chlorine, bromine or iodine, and 2halogen atoms in the same dihalo-aromatic compound may be the same ordifferent from each other. In one embodiment, o-dichlorobenzene,m-dichlorobenzene, p-dichlorobenzene or a mixture of 2 or more compoundsthereof is used as the dihalo-aromatic compound.

As is known in the art, it is also possible to use a monohalo compound(not necessarily an aromatic compound) in combination with thedihaloaromatic compound in order to form end groups of the polyarylenesulfide or to regulate the polymerization reaction and/or the molecularweight of the polyarylene sulfide.

The polyarylene sulfide may be a homopolymer or may be a copolymer. By asuitable, selective combination of dihaloaromatic compounds, apolyarylene sulfide copolymer can be formed containing not less than twodifferent units. For instance, in the case where p-dichlorobenzene isused in combination with m-dichlorobenzene or4,4′-dichlorodiphenylsulfone, a polyarylene sulfide copolymer can beformed containing segments having the structure of formula (II):

and segments having the structure of formula (III):

or segments having the structure of formula (IV):

In general, the amount of the dihaloaromatic compound(s) per mole of theeffective amount of the charged alkali metal sulfide can generally befrom 1.0 to 2.0 moles, from 1.05 to 2.0 moles, or from 1.1 to 1.7 moles.Thus, the polyarylene sulfide can include alkyl halide (generally alkylchloride) end groups.

A process for producing the polyarylene sulfide can include carrying outthe polymerization reaction in an organic amide solvent. Exemplaryorganic amide solvents used in a polymerization reaction can include,without limitation, N-methyl-2-pyrrolidone; N-ethyl-2-pyrrolidone;N,N-dimethylformamide; N,N-dimethylacetamide; N-methylcaprolactam;tetramethylurea; dimethylimidazolidinone; hexamethyl phosphoric acidtriamide and mixtures thereof. The amount of the organic amide solventused in the reaction can be, e.g., from 0.2 to 5 kilograms per mole(kg/mol) of the effective amount of the alkali metal sulfide.

The polymerization can be carried out by a step-wise polymerizationprocess. The first polymerization step can include introducing thedihaloaromatic compound to a reactor, and subjecting the dihaloaromaticcompound to a polymerization reaction in the presence of water at atemperature of from about 180° C. to about 235° C., or from about 200°C. to about 230° C., and continuing polymerization until the conversionrate of the dihaloaromatic compound attains to not less than about 50mol % of the theoretically necessary amount.

In a second polymerization step, water is added to the reaction slurryso that the total amount of water in the polymerization system isincreased to about 7 moles, or to about 5 moles, per mole of theeffective amount of the charged alkali metal sulfide. Following, thereaction mixture of the polymerization system can be heated to atemperature of from about 250° C. to about 290° C., from about 255° C.to about 280° C., or from about 260° C. to about 270° C. and thepolymerization can continue until the melt viscosity of the thus formedpolymer is raised to the desired final level of the polyarylene sulfide.The duration of the second polymerization step can be, e.g., from about0.5 to about 20 hours, or from about 1 to about 10 hours.

The polyarylene sulfide may be linear, semi-linear, branched orcrosslinked. A linear polyarylene sulfide includes as the mainconstituting unit the repeating unit of —(Ar—S)—. In general, a linearpolyarylene sulfide may include about 80 mol % or more of this repeatingunit. A linear polyarylene sulfide may include a small amount of abranching unit or a cross-linking unit, but the amount of branching orcross-linking units may be less than about 1 mol % of the total monomerunits of the polyarylene sulfide. A linear polyarylene sulfide polymermay be a random copolymer or a block copolymer containing theabove-mentioned repeating unit.

A semi-linear polyarylene sulfide may be utilized that may have across-linking structure or a branched structure provided by introducinginto the polymer a small amount of one or more monomers having three ormore reactive functional groups. For instance between about 1 mol % andabout 10 mol % of the polymer may be formed from monomers having threeor more reactive functional groups. Methods that may be used in makingsemi-linear polyarylene sulfide are generally known in the art. By wayof example, monomer components used in forming a semi-linear polyarylenesulfide can include an amount of polyhaloaromatic compounds having 2 ormore halogen substituents per molecule which can be utilized inpreparing branched polymers. Such monomers can be represented by theformula R′X_(n), where each X is selected from chlorine, bromine, andiodine, n is an integer of 3 to 6, and R′ is a polyvalent aromaticradical of valence n which can have up to about 4 methyl substituents,the total number of carbon atoms in R′ being within the range of 6 toabout 16. Examples of some polyhaloaromatic compounds having more thantwo halogens substituted per molecule that can be employed in forming asemi-linear polyarylene sulfide include 1,2,3-trichlorobenzene,1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene,1,2,4-triiodobenzene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene,1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2′,4,4′-tetrachlorobiphenyl,2,2′,5,5′-tetra-iodobiphenyl,2,2′,6,6′-tetrabromo-3,3′,5,5′-tetramethylbiphenyl,1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, andthe like, and mixtures thereof.

Following polymerization, the polyarylene sulfide may be washed withliquid media. For instance, the polyarylene sulfide may be washed withwater and/or organic solvents that will not decompose the polyarylenesulfide including, without limitation, acetone, N-methyl-2-pyrrolidone,a salt solution, and/or an acidic media such as acetic acid orhydrochloric acid prior to combination with other components whileforming the mixture. The polyarylene sulfide can be washed in asequential manner that is generally known to persons skilled in the art.Washing with an acidic solution or a salt solution may reduce thesodium, lithium or calcium metal ion end group concentration from about2000 ppm to about 100 ppm.

A polyarylene sulfide can be subjected to a hot water washing process.The temperature of a hot water wash can be at or above about 100° C.,for instance higher than about 120° C., higher than about 150° C., orhigher than about 170° C.

The polymerization reaction apparatus for forming the polyarylenesulfide is not especially limited, although it is typically desired toemploy an apparatus that is commonly used in formation of high viscosityfluids. Examples of such a reaction apparatus may include a stirringtank type polymerization reaction apparatus having a stirring devicethat has a variously shaped stirring blade, such as an anchor type, amultistage type, a spiral-ribbon type, a screw shaft type and the like,or a modified shape thereof. Further examples of such a reactionapparatus include a mixing apparatus commonly used in kneading, such asa kneader, a roll mill, a Banbury mixer, etc. Following polymerization,the molten polyarylene sulfide may be discharged from the reactor,typically through an extrusion orifice fitted with a die of desiredconfiguration, cooled, and collected. Commonly, the polyarylene sulfidemay be discharged through a perforated die to form strands that aretaken up in a water bath, pelletized and dried. The polyarylene sulfidemay also be in the form of a strand, granule, or powder.

As stated, formation of the polyarylene sulfide is not a requirement,and a polyarylene sulfide can also be purchased from known suppliers.For instance Fortron® polyphenylene sulfide available from Ticona ofFlorence, Ky., USA can be purchased and utilized as the polyarylenesulfide.

The polyarylene sulfide composition may include the polyarylene sulfidecomponent (which also encompasses a blend of polyarylene sulfides) in anamount from about 10 wt. % to about 99 wt. % by weight of thecomposition, for instance from about 20% wt. % to about 90 wt. % byweight of the composition.

The polyarylene sulfide may be of any suitable molecular weight and meltviscosity, generally depending upon the final application intended forthe polyarylene sulfide composition. For instance, the melt viscosity ofthe polyarylene sulfide may be a low viscosity polyarylene sulfide,having a melt viscosity of less than about 500 poise, a medium viscositypolyarylene sulfide, having a melt viscosity of between about 500 poiseand about 1500 poise, or a high melt viscosity polyarylene sulfide,having a melt viscosity of greater than about 1,500 poise, as determinedin accordance with ISO Test No. 11443 at a shear rate of 1200 s⁻¹ and ata temperature of 310° C.

According to one embodiment, the polyarylene sulfide can befunctionalized to further encourage bond formation between thepolyarylene sulfide and the impact modifier. For instance, a polyarylenesulfide can be further treated following formation with a carboxyl, acidanhydride, amine, isocyanate or other functional group-containingmodifying compound to provide a functional terminal group on thepolyarylene sulfide. By way of example, a polyarylene sulfide can bereacted with a modifying compound containing a mercapto group or adisulfide group and also containing a reactive functional group. In oneembodiment, the polyarylene sulfide can be reacted with the modifyingcompound in an organic solvent. In another embodiment, the polyarylenesulfide can be reacted with the modifying compound in the molten state.

In one embodiment, a disulfide compound containing the desiredfunctional group can be incorporated into the polyarylene sulfidecomposition formation process, and the polyarylene sulfide can befunctionalized in conjunction with formation of the composition. Forinstance, a disulfide compound containing the desired reactivefunctional groups can be added to the melt extruder in conjunction withthe polyarylene sulfide or at any other point prior to or in conjunctionwith the addition of the crosslinking agent.

Reaction between the polyarylene sulfide polymer and the reactivelyfunctionalized disulfide compound can include chain scission of thepolyarylene sulfide polymer that can decrease melt viscosity of thepolyarylene sulfide. In one embodiment, a higher melt viscositypolyarylene sulfide having low halogen content can be utilized as astarting polymer. Following reactive functionalization of thepolyarylene sulfide polymer by use of a functional disulfide compound, arelatively low melt viscosity polyarylene sulfide with low halogencontent can be formed. Following this chain scission, the melt viscosityof the polyarylene sulfide can be suitable for further processing, andthe overall halogen content of the low melt viscosity polyarylenesulfide can be quite low. A polyarylene sulfide composition thatexhibits excellent strength and degradation resistance in addition tolow halogen content can be advantageous as low halogen content polymericmaterials are becoming increasingly desired due to environmentalconcerns. In one embodiment, the polyarylene sulfide composition canhave a halogen content of less than about 1000 ppm, less than about 900ppm, less than about 600 ppm, or less than about 400 ppm as determinedaccording to an elemental analysis using Parr Bomb combustion followedby Ion Chromatography.

The disulfide compound can generally have the structure of:R¹—S—S—R²wherein R¹ and R² may be the same or different and are hydrocarbongroups that independently include from 1 to about 20 carbons. Forinstance, R¹ and R² may be an alkyl, cycloalkyl, aryl, or heterocyclicgroup. R¹ and R¹ may include reactive functionality at terminal end(s)of the disulfide compound. For example, at least one of R¹ and R² mayinclude a terminal carboxyl group, hydroxyl group, a substituted ornon-substituted amino group, a nitro group, or the like. In general, thereactive functionality can be selected such that the reactivelyfunctionalized polyarylene sulfide can react with the impact modifier.For example, when considering an epoxy-terminated impact modifier, thedisulfide compound can include carboxyl and/or amine functionality.

Examples of disulfide compounds including reactive terminal groups asmay be encompassed herein may include, without limitation,2,2′-diaminodiphenyl disulfide, 3,3′-diaminodiphenyl disulfide,4,4′-diaminodiphenyl disulfide, dibenzyl disulfide, dithiosalicyclicacid, dithioglycolic acid, α,α′-dithiodilactic acid, β,β′-dithiodilacticacid, 3,3′-dithiodipyridine, 4,4′dithiomorpholine,2,2′-dithiobis(benzothiazole), 2,2′-dithiobis(benzimidazole),2,2′-dithiobis(benzoxazole) and 2-(4′-morpholinodithio)benzothiazole.

The ratio of the amount of the polyarylene sulfide to the amount of thedisulfide compound can be from about 1000:1 to about 10:1, from about500:1 to about 20:1, or from about 400:1 to about 30:1.

In addition to the polyarylene sulfide polymer, the composition alsoincludes an impact modifier. More specifically, the impact modifier canbe an olefinic copolymer or terpolymer. For instance, the impactmodifier can include ethylenically unsaturated monomer units have fromabout 4 to about 10 carbon atoms.

The impact modifier can be modified to include functionalization so asto react with the crosslinking agent. For instance, the impact modifiercan be modified with a mole fraction of from about 0.01 to about 0.5 ofone or more of the following: an α, β unsaturated dicarboxylic acid orsalt thereof having from about 3 to about 8 carbon atoms; an α, βunsaturated carboxylic acid or salt thereof having from about 3 to about8 carbon atoms; an anhydride or salt thereof having from about 3 toabout 8 carbon atoms; a monoester or salt thereof having from about 3 toabout 8 carbon atoms; a sulfonic acid or a salt thereof; an unsaturatedepoxy compound having from about 4 to about 11 carbon atoms. Examples ofsuch modification functionalities include maleic anhydride, fumaricacid, maleic acid, methacrylic acid, acrylic acid, and glycidylmethacrylate. Examples of metallic acid salts include the alkaline metaland transitional metal salts such as sodium, zinc, and aluminum salts.

A non-limiting listing of impact modifiers that may be used includeethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymers,ethylene-alkyl (meth)acrylate-maleic anhydride terpolymers,ethylene-alkyl (meth)acrylate-glycidyl (meth)acrylate terpolymers,ethylene-acrylic ester-methacrylic acid terpolymer, ethylene-acrylicester-maleic anhydride terpolymer, ethylene-methacrylic acid-methacrylicacid alkaline metal salt (ionomer) terpolymers, and the like. In oneembodiment, for instance, an impact modifier can include a randomterpolymer of ethylene, methylacrylate, and glycidyl methacrylate. Theterpolymer can have a glycidyl methacrylate content of from about 5% toabout 20%, such as from about 6% to about 10%. The terpolymer may have amethylacrylate content of from about 20% to about 30%, such as about24%.

According to one embodiment, the impact modifier may be a linear orbranched, homopolymer or copolymer (e.g., random, graft, block, etc.)containing epoxy functionalization, e.g., terminal epoxy groups,skeletal oxirane units, and/or pendent epoxy groups. For instance, theimpact modifier may be a copolymer including at least one monomercomponent that includes epoxy functionalization. The monomer units ofthe impact modifier may vary. In one embodiment, for example, the impactmodifier can include epoxy-functional methacrylic monomer units. As usedherein, the term methacrylic generally refers to both acrylic andmethacrylic monomers, as well as salts and esters thereof, e.g.,acrylate and methacrylate monomers. Epoxy-functional methacrylicmonomers as may be incorporated in the impact modifier may include, butare not limited to, those containing 1,2-epoxy groups, such as glycidylacrylate and glycidyl methacrylate. Other suitable epoxy-functionalmonomers include allyl glycidyl ether, glycidyl ethacrylate, andglycidyl itoconate.

Other monomer units may additionally or alternatively be a component ofthe impact modifier. Examples of other monomers may include, forexample, ester monomers, olefin monomers, amide monomers, etc. In oneembodiment, the impact modifier can include at least one linear orbranched α-olefin monomer, such as those having from 2 to 20 carbonatoms, or from 2 to 8 carbon atoms. Specific examples include ethylene;propylene; 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene;1-pentene; 1-pentene with one or more methyl, ethyl or propylsubstituents; 1-hexene with one or more methyl, ethyl or propylsubstituents; 1-heptene with one or more methyl, ethyl or propylsubstituents; 1-octene with one or more methyl, ethyl or propylsubstituents; 1-nonene with one or more methyl, ethyl or propylsubstituents; ethyl, methyl or dimethyl-substituted 1-decene;1-dodecene; and styrene.

Monomers included in an impact modifier that includes epoxyfunctionalization can include monomers that do not include epoxyfunctionalization, as long as at least a portion of the monomer units ofthe polymer are epoxy functionalized.

In one embodiment, the impact modifier can be a terpolymer that includesepoxy functionalization. For instance, the impact modifier can include amethacrylic component that includes epoxy functionalization, an α-olefincomponent, and a methacrylic component that does not include epoxyfunctionalization. For example, the impact modifier may bepoly(ethylene-co-methylacrylate-co-glycidyl methacrylate), which has thefollowing structure:

wherein, a, b, and c are 1 or greater.

In another embodiment the impact modifier can be a random copolymer ofethylene, ethyl acrylate and maleic anhydride having the followingstructure:

wherein x, y and z are 1 or greater.

The relative proportion of the various monomer components of acopolymeric impact modifier is not particularly limited. For instance,in one embodiment, the epoxy-functional methacrylic monomer componentscan form from about 1 wt. % to about 25 wt. %, or from about 2 wt. % toabout 20 wt % of a copolymeric impact modifier. An α-olefin monomer canform from about 55 wt. % to about 95 wt. %, or from about 60 wt. % toabout 90 wt. %, of a copolymeric impact modifier. When employed, othermonomeric components (e.g., a non-epoxy functional methacrylic monomers)may constitute from about 5 wt. % to about 35 wt. %, or from about 8 wt.% to about 30 wt. %, of a copolymeric impact modifier.

An impact modifier may be formed according to standard polymerizationmethods as are generally known in the art. For example, a monomercontaining polar functional groups may be grafted onto a polymerbackbone to form a graft copolymer. Alternatively, a monomer containingfunctional groups may be copolymerized with a monomer to form a block orrandom copolymer using known free radical polymerization techniques,such as high pressure reactions, Ziegler-Natta catalyst reactionsystems, single site catalyst (e.g., metallocene) reaction systems, etc.

Alternatively, an impact modifier may be obtained on the retail market.By way of example, suitable compounds for use as an impact modifier maybe obtained from Arkema under the name Lotader®.

The molecular weight of the impact modifier can vary widely. Forexample, the impact modifier can have a number average molecular weightfrom about 7,500 to about 250,000 grams per mole, in some embodimentsfrom about 15,000 to about 150,000 grams per mole, and in someembodiments, from about 20,000 to 100,000 grams per mole, with apolydispersity index typically ranging from 2.5 to 7.

In general, the impact modifier may be present in the composition in anamount from about 0.05% to about 40% by weight, from about 0.05% toabout 37% by weight, or from about 0.1% to about 35% by weight.

Referring again to FIG. 1, the impact modifier can be added to thecomposition in conjunction with the polyarylene sulfide composition atthe main feed throat 14 of the melt processing unit. This is not arequirement of the composition formation process, however, and in otherembodiments, the impact modifier can be added downstream of the mainfeed throat. For instance, the impact modifier may be added at alocation downstream from the point at which the polyarylene sulfide issupplied to the melt processing unit, but yet prior to the meltingsection, i.e., that length of the melt processing unit in which thepolyarylene sulfide becomes molten. In another embodiment, the impactmodifier may be added at a location downstream from the point at whichthe polyarylene sulfide becomes molten.

If desired, one or more distributive and/or dispersive mixing elementsmay be employed within the mixing section of the melt processing unit.Suitable distributive mixers for single screw extruders may include butare not limited to, for instance, Saxon, Dulmage, Cavity Transfermixers, etc. Likewise, suitable dispersive mixers may include but arenot limited to Blister ring, Leroy/Maddock, CRD mixers, etc. As is wellknown in the art, the mixing may be further improved by using pins inthe barrel that create a folding and reorientation of the polymer melt,such as those used in Buss Kneader extruders, Cavity Transfer mixers,and Vortex Intermeshing Pin mixers.

In addition to the polyarylene sulfide and the impact modifier, thepolyarylene composition can include a crosslinking agent. Thecrosslinking agent can be a polyfunctional compound or combinationthereof that can react with functionality of the impact modifier to formcrosslinks within and among the polymer chains of the impact modifier.In general, the crosslinking agent can be a non-polymeric compound,i.e., a molecular compound that includes two or more reactivelyfunctional terminal moieties linked by a bond or a non-polymeric(non-repeating) linking component. By way of example, the crosslinkingagent can include but is not limited to di-epoxides, poly-functionalepoxides, diisocyanates, polyisocyanates, polyhydric alcohols,water-soluble carbodiimides, diamines, diaminoalkanes, polyfunctionalcarboxylic acids, diacid halides, and so forth. For instance, whenconsidering an epoxy-functional impact modifier, a non-polymericpolyfunctional carboxylic acid or amine can be utilized as acrosslinking agent.

Specific examples of polyfunctional carboxylic acid crosslinking agentscan include, without limitation, isophthalic acid, terephthalic acid,phthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenylether, 4,4′-bisbenzoic acid, 1,4- or 1,5-naphthalene dicarboxylic acids,decahydronaphthalene dicarboxylic acids, norbornene dicarboxylic acids,bicyclooctane dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid (bothcis and trans), 1,4-hexylenedicarboxylic acid, adipic acid, azelaicacid, dicarboxyl dodecanoic acid, succinic acid, maleic acid, glutaricacid, suberic acid, azelaic acid and sebacic acid. The correspondingdicarboxylic acid derivatives, such as carboxylic acid diesters havingfrom 1 to 4 carbon atoms in the alcohol radical, carboxylic acidanhydrides or carboxylic acid halides may also be utilized.

Exemplary diols useful as crosslinking agents can include, withoutlimitation, aliphatic diols such as ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propane diol,2-ethyl-2-methyl-1,3-propane diol, 1,4-butane diol, 1,4-but-2-ene diol,1,3-1,5-pentane diol, 1,5-pentane diol, dipropylene glycol,2-methyl-1,5-pentane diol, and the like. Aromatic diols can also beutilized such as, without limitation, hydroquinone, catechol,resorcinol, methylhydroquinone, chlorohydroquinone, bisphenol A,tetrachlorobisphenol A, phenolphthalein, and the like. Exemplarycycloaliphatic diols as may be used include a cycloaliphatic moiety, forexample 1,6-hexane diol, dimethanol decalin, dimethanol bicyclooctane,1,4-cyclohexane dimethanol (including its cis- and trans-isomers),triethylene glycol, 1,10-decanediol, and the like.

Exemplary diamines that may be utilized as crosslinking agents caninclude, without limitation, isophorone-diamine, ethylenediamine, 1,2-,1,3-propylene-diamine, N-methyl-1,3-propylene-diamine,N,N′-dimethyl-ethylene-diamine, and aromatic diamines, such as, forexample, 2,4- and 2,6-toluoylene-diamine, 3,5-diethyl-2,4- and/or-2,6-toluoylene-diamine, and primary ortho- di-, tri- and/ortetra-alkyl-substituted 4,4′-diaminodiphenyl-methanes, (cyclo)aliphaticdiamines, such as, for example, isophorone-diamine, ethylenediamine,1,2-, 1,3-propylene-diamine, N-methyl-1,3-propylene-diamine,N,N′-dimethyl-ethylene-diamine, and aromatic diamines, such as, forexample, 2,4- and 2,6-toluoylene-diamine, 3,5-diethyl-2,4- and/or-2,6-toluoylene-diamine, and primary ortho- di-, tri- and/ortetra-alkyl-substituted 4,4′-diaminodiphenyl-methanes.

In one embodiment, the composition can include a disulfide-freecrosslinking agent. For example, the crosslinking agent can includecarboxyl and/or amine functionality with no disulfide group that mayreact with the polyarylene sulfide. A crosslinking agent that isdisulfide-free can be utilized so as to avoid excessive chain scissionof the polyarylene sulfide by the crosslinking agent during formation ofthe composition. It should be understood, however, that the utilizationof a disulfide-free crosslinking agent does not in any way limit theutilization of a reactively functionalized disulfide compound forfunctionalizing the polyarylene sulfide. For instance, in oneembodiment, the composition can be formed according to a process thatincludes addition of a reactively functionalized disulfide compound tothe melt processing unit that can reactively functionalize thepolyarylene sulfide. The crosslinking agent utilized in this embodimentcan then be a disulfide-free crosslinking agent that can includefunctionality that is reactive with the impact modifier as well as withthe reactively functionalized polyarylene sulfide. Thus, the compositioncan be highly crosslinked without excessive scission of the polyarylenesulfide polymer chains.

In another embodiment the crosslinking agent and the polyarylene sulfidefunctionalization compound (when present) can be selected so as toencourage chain scission of the polyarylene sulfide. This may bebeneficial, for instance, which chain scission is desired to decreasethe melt viscosity of the polyarylene sulfide polymer.

The polyarylene sulfide composition may generally include thecrosslinking agent in an amount from about 0.05 wt. % to about 2 wt. %by weight of the polyarylene sulfide composition, from about 0.07 wt. %to about 1.5 wt. % by weight of the polyarylene sulfide composition, orfrom about 0.1 wt. % to about 1.3 wt. %.

The crosslinking agent can be added to the melt processing unitfollowing mixing of the polyarylene sulfide and the impact modifier. Forinstance, as illustrated in FIG. 1, the crosslinking agent can be addedto the composition at a downstream location 16 following addition ofpolyarylene sulfide and the impact modifier (either together orseparately) to the melt processing unit. This can ensure that the impactmodifier has become dispersed throughout the polyarylene sulfide priorto addition of the crosslinking agent.

To help encourage distribution of the impact modifier throughout themelt prior to addition of the crosslinking agent, a variety of differentparameters may be selectively controlled. For example, the ratio of thelength (“L”) to diameter (“D”) of a screw of the melt processing unitmay be selected to achieve an optimum balance between throughput andimpact modifier distribution. For example, the L/D value after the pointat which the impact modifier is supplied may be controlled to encouragedistribution of the impact modifier. More particularly, the screw has ablending length (“L_(B)”) that is defined from the point at which boththe impact modifier and the polyarylene sulfide are supplied to the unit(i.e., either where they are both supplied in conjunction with oneanother or the point at which the latter of the two is supplied) to thepoint at which the crosslinking agent is supplied, the blending lengthgenerally being less than the total length of the screw. For example,when considering a melt processing unit that has an overall L/D of 40,the L_(B)/D ratio of the screw can be from about 1 to about 36, in someembodiments from about 4 to about 20, and in some embodiments, fromabout 5 to about 15. In one embodiment, the L/L_(B) ratio can be fromabout 40 to about 1.1, from about 20 to about 2, or from about 10 toabout 5.

Following addition of the crosslinking agent, the composition can bemixed to distribute the crosslinking agent throughout the compositionand encourage reaction between the crosslinking agent, the impactmodifier, and, in one embodiment, with the polyarylene sulfide.

The composition can also include one or more additives as are generallyknown in the art. For example, one or more fillers can be included inthe polyarylene sulfide composition. One or more fillers may generallybe included in the polyarylene sulfide composition an amount of fromabout 5 wt. % to about 70 wt. %, or from about 20 wt. % to about 65 wt.% by weight of the polyarylene sulfide composition.

The filler can be added to the polyarylene sulfide composition accordingto standard practice. For instance, the filler can be added to thecomposition at a downstream location of the melt processing unit. Forexample, a filler may be added to the composition in conjunction withthe addition of the crosslinking agent. However, this is not arequirement of a formation process and the filler can be addedseparately from the crosslinking agent and either upstream or downstreamof the point of addition of the crosslinking agent. In addition, afiller can be added at a single feed location, or may be split and addedat multiple feed locations along the melt processing unit.

In one embodiment, a fibrous filler can be included in the polyarylenesulfide composition. The fibrous filler may include one or more fibertypes including, without limitation, polymer fibers, glass fibers,carbon fibers, metal fibers, basalt fibers, and so forth, or acombination of fiber types. In one embodiment, the fibers may be choppedfibers, continuous fibers, or fiber rovings (tows).

Fiber sizes can vary as is known in the art. In one embodiment, thefibers can have an initial length of from about 3 mm to about 5 mm. Inanother embodiment, for instance when considering a pultrusion process,the fibers can be continuous fibers. Fiber diameters can vary dependingupon the particular fiber used. The fibers, for instance, can have adiameter of less than about 100 μm, such as less than about 50 μm. Forinstance, the fibers can be chopped or continuous fibers and can have afiber diameter of from about 5 μm to about 50 μm, such as from about 5μm to about 15 μm.

The fibers may be pretreated with a sizing as is generally known. In oneembodiment, the fibers may have a high yield or small K numbers. The towis indicated by the yield or K number. For instance, glass fiber towsmay have 50 yield and up, for instance from about 115 yield to about1200 yield.

Other fillers can alternatively be utilized or may be utilized inconjunction with a fibrous filler. For instance, a particulate fillercan be incorporated in the polyarylene sulfide composition. In general,particulate fillers can encompass any particulate material having amedian particle size of less than about 750 μm, for instance less thanabout 500 μm, or less than about 100 μm. In one embodiment, aparticulate filler can have a median particle size in the range of fromabout 3 μm to about 20 μm. In addition, a particulate filler can besolid or hollow, as is known. Particulate fillers can also include asurface treatment, as is known in the art.

Particulate fillers can encompass one or more mineral fillers. Forinstance, the polyarylene sulfide composition can include one or moremineral fillers in an amount of from about 1 wt. % to about 60 wt. % ofthe composition. Mineral fillers may include, without limitation,silica, quartz powder, silicates such as calcium silicate, aluminumsilicate, kaolin, talc, mica, clay, diatomaceous earth, wollastonite,calcium carbonate, and so forth.

When incorporating multiple fillers, for instance a particulate fillerand a fibrous filler, the fillers may be added together or separately tothe melt processing unit. For instance, a particulate filler can beadded to the main feed with the polyarylene sulfide or downstream priorto addition of a fibrous filler, and a fibrous filler can be addedfurther downstream of the addition point of the particulate filler. Ingeneral, a fibrous filler can be added downstream of any other fillerssuch as a particulate filler, though this is not a requirement.

A filler can be an electrically conductive filler such as, withoutlimitation, carbon black, graphite, graphene, carbon fiber, carbonnanotubes, a metal powder, and so forth. In those embodiments in whichthe polyarylene sulfide composition includes electrically conductivefillers, for instance when the polyarylene sulfide composition isutilized in forming a fuel line, adequate electrically conductive fillercan be included such that the composition has a volume specificresistance of equal to or less than about 10⁹ ohms cm.

In one embodiment, the polyarylene sulfide composition can include a UVstabilizer as an additive. For instance, the polyarylene sulfidecomposition can include a UV stabilizer in an amount of between about0.5 wt. % and about 15 wt. %, between about 1 wt. % and about 8 wt. %,or between about 1.5 wt. % and about 7 wt. % of a UV stabilizer. Oneparticularly suitable UV stabilizer that may be employed is a hinderedamine UV stabilizer. Suitable hindered amine UV stabilizer compounds maybe derived from a substituted piperidine, such as alkyl-substitutedpiperidyl, piperidinyl, piperazinone, alkoxypiperidinyl compounds, andso forth. For example, the hindered amine may be derived from a2,2,6,6-tetraalkylpiperidinyl. The hindered amine may, for example, bean oligomeric or polymeric compound having a number average molecularweight of about 1,000 or more, in some embodiments from about 1000 toabout 20,000, in some embodiments from about 1500 to about 15,000, andin some embodiments, from about 2000 to about 5000. Such compoundstypically contain at least one 2,2,6,6-tetraalkylpiperidinyl group(e.g., 1 to 4) per polymer repeating unit. One particularly suitablehigh molecular weight hindered amine is commercially available fromClariant under the designation Hostavin® N30 (number average molecularweight of 1200). Another suitable high molecular weight hindered amineis commercially available from Adeka Palmarole SAS under the designationADK STAB® LA-63 and ADK STAB® LA-68.

In addition to the high molecular hindered amines, low molecular weighthindered amines may also be employed. Such hindered amines are generallymonomeric in nature and have a molecular weight of about 1000 or less,in some embodiments from about 155 to about 800, and in someembodiments, from about 300 to about 800.

Other suitable UV stabilizers may include UV absorbers, such asbenzotriazoles or benzopheones, which can absorb UV radiation.

An additive that may be included in a polyarylene sulfide composition isone or more colorants as are generally known in the art. For instance,the polyarylene sulfide composition can include from about 0.1 wt. % toabout 10 wt. %, or from about 0.2 wt. % to about 5 wt. % of one or morecolorants. As utilized herein, the term “colorant” generally refers toany substance that can impart color to a material. Thus, the term“colorant” encompasses both dyes, which exhibit solubility in an aqueoussolution, and pigments, that exhibit little or no solubility in anaqueous solution.

Examples of dyes that may be used include, but are not limited to,disperse dyes. Suitable disperse dyes may include those described in“Disperse Dyes” in the Color Index, 3^(rd) edition. Such dyes include,for example, carboxylic acid group-free and/or sulfonic acid group-freenitro, amino, aminoketone, ketoninime, methine, polymethine,diphenylamine, quinoline, benzimidazole, xanthene, oxazine and coumarindyes, anthraquinone and azo dyes, such as mono- or di-azo dyes. Dispersedyes also include primary red color disperse dyes, primary blue colordisperse dyes, and primary yellow color dyes.

Pigments that can be incorporated in a polyarylene sulfide compositioncan include, without limitation, organic pigments, inorganic pigments,metallic pigments, phosphorescent pigments, fluorescent pigments,photochromic pigments, thermochromic pigments, iridescent pigments, andpearlescent pigments. The specific amount of pigment can depends uponthe desired final color of the product. Pastel colors are generallyachieved with the addition of titanium dioxide white or a similar whitepigment to a colored pigment.

Other additives that can be included in the polyarylene sulfidecomposition can encompass, without limitation, antimicrobials,lubricants, pigments or other colorants, impact modifiers, antioxidants,stabilizers (e.g., heat stabilizers including organophosphites such asDoverphos® products available from Dover Chemical Corporation),surfactants, flow promoters, solid solvents, and other materials addedto enhance properties and processability. Such optional materials may beemployed in the polyarylene sulfide composition in conventional amountsand according to conventional processing techniques, for instancethrough addition to the polyarylene sulfide composition at the main feedthroat. Beneficially, the polyarylene sulfide composition can exhibitdesirable characteristics without the addition of plasticizers. Forinstance, the composition can be free of plasticizers such as phthalateesters, trimellitates, sebacates, adipates, gluterates, azelates,maleates, benzoates, and so forth.

Following addition of all components to the polyarylene sulfidecomposition, the composition is thoroughly mixed in the remainingsection(s) of the extruder and extruded through a die. The finalextrudate can be pelletized or other wise shaped as desired, forinstance the final extrudate can be in the form of a pultruded tape orribbon.

Conventional shaping processes can be used for forming articles out ofthe polyarylene sulfide composition including, without limitation,extrusion, injection molding, blow-molding, thermoforming, foaming,compression molding, hot-stamping, fiber spinning and so forth. Shapedarticles that may be formed may include structural and non-structuralshaped parts, for instance components for automotive engineeringthermoplastic assemblies as well as industrial applications such ascomponents of cooling tower pumps, water heaters, and the like. Forinstance thermoform sheets, foamed substrates, injection molded or blowmolded components, and the like can be formed from the polyarylenesulfide composition.

Tubular members as may be utilized for carrying liquids or gases, and inone particular embodiment heated liquids or gases, may be formed fromthe polyarylene sulfide composition. For instance tubular membersincluding hoses, pipes, conduits and the like can be formed from thepolyarylene sulfide composition. The tubular members may besingle-layered or multi-layered. Typical conventional extrusion ormolding processes may be used for forming the tubular members. Forinstance, either single or multi-screw extruders may be used forextrusion of the tubing. In another embodiment, a blow molding processmay be utilized in forming a tubular hollow member.

Referring to FIG. 2, one embodiment of a tubular member 110 formed fromthe polyarylene sulfide composition is shown. As shown, the tubularmember 110 extends in multiple directions leading to a relativelycomplex shape. For instance, before the polyarylene sulfide compositioncan solidify, the angular displacements as shown in FIG. 2 can be formedinto the part. The tubular member 110 includes angular displacementchanges at 112, 114 and 116. The tubular member 110 may comprise, forinstance, a part that may be used in the exhaust system of a vehicle.

A component can include the polyarylene sulfide composition throughoutthe entire component or only a portion of the component. For instance,when considering a component having a large aspect ratio (L/D>1), suchas a fiber or a tubular member, the component can be formed such thatthe polyarylene sulfide composition extends along a section of thecomponent and an adjacent section can be formed of a differentcomposition, for instance a different polyarylene sulfide composition.Such a component can be formed by, e.g., altering the material that isfed to a molding device during a formation process. The component caninclude an area in which the two materials are mixed that represents aborder region between a first section and a second section formed ofdifferent materials. A component can include a single section formed ofthe polyarylene sulfide composition or a plurality of sections, asdesired. Moreover, other sections of a component can be formed ofmultiple different materials. By way of example, when considering atubular component such as a fluid conduit, both ends of the tubularcomponent can be formed of the polyarylene sulfide composition and acenter section can be formed of a less flexible composition. Thus, themore flexible ends can be utilized to tightly affix the component toother components of a system. Alternatively, a center section of acomponent could be formed from the polyarylene sulfide composition,which can improve flexibility of the component in that section, makinginstallation of the component easier.

According to one embodiment, the tubular member such as the tubularmember 110 illustrated in FIG. 2 can be a single layer tubular memberformed according to a blow molding process. FIG. 3 illustrates onemethod as may be utilized for forming a component from the polyarylenesulfide composition. It should be understood, however, that while theblow molding process illustrates in FIG. 3 includes the formation of atubular member, blow molding methodology can be utilized in forming awide variety of shaped devices, and is in no way intended to be limitedto tubular components formed of the polyarylene sulfide composition.

During blow molding, the polyarylene sulfide composition is first heatedand extruded into a parison 1020 using a die attached to an extrusiondevice. When the parison 1020 is formed, the composition must havesufficient melt strength to prevent gravity from undesirably elongatingportions of the parison 1020 and thereby forming non-uniform wallthicknesses and other imperfections. The parison is received into amolding device 1026, generally formed of multiple sections 1028, 1030,1040, 1042 that together form a three-dimensional mold cavity 1026. Forinstance, a robotic arm 1024 can be utilized to manipulate the parison1020 in the molding device.

As can be appreciated, a certain period of time elapses from formationof the parison 1020 to moving the parison into engagement with themolding device. During this stage of the process, the melt strength ofthe polyarylene sulfide composition can be high enough such that theparison 1020 maintains its shape during movement. The polyarylenesulfide composition can also be capable of remaining in a semi-fluidstate and not solidifying too rapidly before blow molding commences.

Once the molding device is closed, a gas, such as an inert gas is fedinto the parison 1020 from a gas supply 1034. The gas suppliessufficient pressure against the interior surface of the parison suchthat the parison conforms to the shape of the mold cavity. After blowmolding, the sections can be opened as indicated by the directionalarrows, and the finished shaped article is then removed. In oneembodiment, cool air can be injected into the molded part forsolidifying the polyarylene sulfide composition prior to removal fromthe molding device.

According to another embodiment illustrated in FIG. 4, a continuous blowmolding process can be used to form a component, such as long tubularcomponents as may be useful in piping applications. FIG. 4 presents aschematic illustration of one method as may be utilized in forming along tubular component according to a continuous blow molding process.In a continuous process, a stationary extruder (not shown) canplasticize and force the molten polyarylene sulfide composition througha head to form a continuous parison 1601. An accumulator 1605 can beused to support the parison 1601 and prevent sagging prior to molding.The parison may be fed to a mold formed of articulated sections 1602,1603 that travel in conjunction with the continuous parison on a moldconveyor assembly 1604. Air under pressure is applied to the parison toblow mold the composition within the mold. After the composition hasbeen molded and sufficiently cooled within the mold as the mold andcomposition travel together, the mold segments are separated from oneanother and the formed section of the component (e.g., the pipe) 1606 isremoved from the conveyor and taken up, as on a take-up reel (notshown).

A tubular member such as a pipe or a tube can be formed according to anextrusion process. For example, an extrusion process utilizing a simpleor barrier type screw can be utilized and, in one embodiment, a mixingtip need not be utilized in the process. The compression ratio for anextrusion process can be between about 2.5:1 and about 4:1. Forinstance, the compression ratio can be about 25% feed, about 25%transition, and about 50% metering. The ratio of the barrel length tothe barrel diameter (L/D) can be from about 16 to about 24. An extrusionprocess can also utilize other standard components as are known in theart such as, for example, breaker plates, screen packs, adapters, a die,and a vacuum tank. The vacuum tank can generally include a sizingsleeve/calibration ring, tank seals, and the like.

When forming a product such as a tubular member according to anextrusion process, the polyarylene sulfide composition can first bedried, for instance at a temperature of from about 90° C. to about 100°C. for about three hours. It may be beneficial to avoid drying for anextensive length of time so as to avoid discoloration of thecomposition. The extruder can exhibit different temperatures indifferent zones, as is known. For instance, in one embodiment, theextruder can include at least four zones, with the temperature of thefirst zone from about 276° C. to about 288° C., the temperature of thesecond zone from about 282° C. to about 299° C., the temperature of thethird zone from about 282° C. to about 299° C., and the temperature ofthe fourth zone from about 540° C. to about 580° C. Meanwhile, thetemperature of the die can be from about 293° C. to about 310° C., andthe vacuum tank water can be from about 20° C. to about 50° C.

Typically, the head pressure can be from about 100 pounds per squareinch (psi) (about 690 kPa) to about 1000 psi (about 6900 kPa), and thehead pressure can be adjusted to achieve a stable melt flow, as isknown. For instance, the head pressure can be reduced by increasing theextruder zone temperature, by increasing the extruder screw rotationsper minute, reducing the screen pack mesh size and/or the number ofscreens, and so forth. In general, the line speed can be from about 4meters per minute to about 15 meters per minute. Of course, the actualline speed can depend upon the final dimension of the final product, theaesthetics of the final product and process stability.

The die swell during an extrusion process can generally be negligible. Adraw down of about 1.2 to about 1.7 can generally be utilized, as ahigher draw down can negatively affect the final properties of theproduct, depending on other processing conditions. Die drool cangenerally be avoided by drying the resin adequately prior to extrusionas well as by maintaining the melt temperature at less than about 304°C.

In one embodiment, tubular members extruded from the polyarylene sulfidecomposition can have a wall thickness of between about 0.5 millimetersto about 5 millimeters, though tubular members having larger wallthickness can be formed from the composition as desired. The calibrationring inner diameter can decide the outer diameter of the tubular memberand will generally be less than the outer diameter of the die, as isknown. The inner diameter of the tubular member can be utilized todetermine the desired outer diameter of the mandrel and the line speed,as is known.

A tubular member that incorporates the polyarylene sulfide compositioncan be a multi-layered tubular member. FIG. 5 illustrates amulti-layered tubular member 210 as may incorporate the polyarylenesulfide composition in one or more layers of the tubular member. Forexample, at least the inner layer 212 can include the polyarylenesulfide composition that exhibits high impact strength characteristicsunder a wide temperature range and which is substantially inert to thematerials to be carried within the tubular member 210.

The outer layer 214 and the intermediate layer 216 can include apolyarylene sulfide composition that is the same or different than thepolyarylene sulfide composition described herein. Alternatively, otherlayers of the multilayer tubular member may be formed of differentmaterials. For example, in one embodiment the intermediate layer 216 canexhibit high resistance to pressure and mechanical effects. By way ofexample, layer 216 can be formed of polyamides from the group ofhomopolyamides, co-polyamides, their blends or mixtures which each otheror with other polymers. Alternatively, layer 216 can be formed of afiber reinforced material such as a fiber-reinforced resin composite orthe like. For example, a polyaramid (e.g., Kevlar®) woven mat can beutilized to form an intermediate layer 216 that is highly resistant tomechanical assaults. An intermediate later can be included such as aspiraled, knitted or braided layer of textile or wire. In a spiralconstruction, for example, the spiraled layer may comprise two layers,each applied at or near the so-called lock angle or neutral angle ofabout 54° with respect to the longitudinal axis of the tubular member210 but with opposite spiral directions. However, the tubular member 210is not limited to spiral constructions. An intermediate layer 216 may bea knit, braided, wrapped, woven, or non-woven fabric.

Outer layer 214 can provide protection from external assaults as well asprovide insulative or other desirable characteristics to the tubularmember. For example, a multi-layer hose can include an outer layer 214formed from an adequate kind of rubber material having high levels ofchipping, weather, flame and cold resistance. Examples of such materialsinclude thermoplastic elastomer such as polyamide thermoplasticelastomer, polyester thermoplastic elastomer, polyolefin thermoplasticelastomer, and styrene thermoplastic elastomer. Suitable materials forouter layer 214 include, without limitation, ethylene-propylene-dieneterpolymer rubber, ethylene-propylene rubber, chlorosulfonatedpolyethylene rubber, a blend of acrylonitrile-butadiene rubber andpolyvinyl chloride, a blend of acrylonitrile-butadiene rubber andethylene-propylene-diene terpolymer rubber, and chlorinated polyethylenerubber.

Outer layer 214 can alternatively be formed of a harder, less flexiblematerial, such as a polyolefin, polyvinylchloride, or a high densitypolyethylene, a fiber reinforced composite material such as a glassfiber composite or a carbon fiber composite, or a metal material such asa steel jacket.

Of course, a multi-layer tubular member is not limited to three layers,and may include two, four, or more distinct layers. A multi-layertubular member may further contain one or more adhesive layers formedfrom adhesive materials such as, for example, polyester polyurethanes,polyether polyurethanes, polyester elastomers, polyether elastomers,polyamides, polyether polyamides, polyether polyimides, functionalizedpolyolefins, and the like.

Multilayer tubular members may be made by conventional processes, suchas, for example, co-extrusion, dry lamination, sandwich lamination,coextrusion coating, blow molding, continuous blow molding, and thelike. By way of example, in forming a three-layered tubular member 210as illustrated in FIG. 5, the polyarylene sulfide composition, apolyamide composition, and a thermoplastic elastomer composition can beseparately fed into three different extruders. The separate extrusionmelts from those three extruders can then be introduced into one dieunder pressure. While producing three different tubular melt flows,those melt flows can be combined in the die in such a manner that themelt flow of the polyarylene sulfide composition forms the inner layer212, that of the polyamide composition forms the intermediate layer 216,and that of the thermoplastic elastomer composition forms the outerlayer 214, and the thus-combined melt flows are co-extruded out of thedie to produce a three-layered tubular member.

Of course, any known tube-forming methods including blow molding methodsas described above is employable. For instance, in one embodiment, oneor more layers of the multi-layered tubular member can be formed from acontinuous tape, e.g., a fiber reinforced tape or ribbon formedaccording to a pultrusion formation method. A tape can be wrapped toform the tubular member or a layer of a multilayered tubular memberaccording to known practices as are generally known in the art.

Tubular members as may be formed from the polyarylene sulfidecomposition can include flow lines for oil and gas, for instance as maybe utilized in off-shore and on-shore oil and gas fields and transport.Flowlines that incorporate the polyarylene sulfide composition may besingle-layered or multi-layered. When considering a multi-layerflowline, the polyarylene sulfide composition can be utilized to form aninner barrier layer of the flowline, but it should be understood thatpolyarylene sulfide composition layers of a multi-layer flowline are inno way limited to barrier layers and one or more other layers of amulti-layer flowline may incorporate the polyarylene sulfidecomposition.

The flowlines can be utilized according to known practice in any gas andoil facility as is generally known in the art. By way of example, FIG. 6illustrates a typical off shore facility including flexible risers 610for conducting production fluid from a subsea facility to a floatingvessel 620. The floating vessel 620 is illustrated floating on a body ofwater having a floor 640. Flexible risers 610 are provided to conveyproduction fluid from a subsea pipeline end manifold 680 through acatenary moored buoy 650 through a yoke 660 to the floating vessel 620.The catenary moored buoy 650 is anchored by anchor lines 630 to anchors672 provided at the floor 640. The pipeline end manifold 680 isconnected by a plurality of flowlines 667 to wells 690.

Flexible risers as illustrated in FIG. 6 can have any suitableconfiguration. By way of example, they can be designed bonded orunbounded risers and can have a steep S or lazy S configuration oralternatively a steep wave or lazy wave configuration as are known inthe art. Standard buoyancy modules 670 as illustrated in FIG. 6 may beutilized in conjunction with the flexible risers to develop the desiredconfiguration as is known. The riser 610 passes over the buoyancy module670 that can include, e.g., a cradle and a buoy. The buoyancy module 670can also be attached to the anchor line 630 so as to support the riser610 and be held in the desired position as determined by the length ofthe anchor line 630 and the riser 610.

FIG. 7 illustrates a typical field that can incorporate a plurality ofdifferent types of flowlines, one or more of which may include at leasta barrier layer formed of the polyarylene sulfide composition. As can beseen, the field can include fixed risers 91 that can carry productionfluid from the sea floor 92 to a platform 95. The field can includeinfield flowlines 93 that can carry production fluid, supporting fluids,umbilicals, etc., within the field. In addition, both the risers 91 andthe infield flowlines 93 can be bundled lines as discussed above. Thesystem also includes a plurality of tie-ins 94 at which point differentflowlines can be merged, for instance to form a bundled riser and/orwhere individual flowlines may be altered, for instance throughexpansion. The system also includes a plurality of satellite wells 98from which the hydrocarbon production fluid is obtained and manifolds.An export pipeline 97 can carry production fluid from the platform 95 toshore, a storage facility, or a transport vessel. The export pipeline 97may also include one or more crossings 96 to by-pass other flowlines,e.g., another pipeline 99.

Referring to FIG. 8, one embodiment of a flexible riser 800 that canincorporate the polyarylene sulfide composition is illustrated. Asshown, the riser 800 has several concentric layers. An innermost layeris generally termed the carcass 802 and can be formed of helically woundstainless steel strip so as to provide resistance against externalpressures. The carcass 802 is generally a metal (e.g., stainless steel)tube that supports the adjacent barrier layer 806 and prevents risercollapse due to pressure or loads applied during operation. The bore ofthe flexible riser 800 can vary depending upon the fluid to be carriedby the riser. For instance, the riser 800 can have a smooth bore whenintended for use to carry a supporting fluid such as an injection fluid(e.g., water and/or methanol) and can have a rough bore when utilized tocarry production fluids (e.g., oil and gas). The carcass, when present,can generally be between about 5 and about 10 millimeters in thickness.According to one embodiment, the carcass can be formed by helicallywound stainless steel strips that interlock with one another to form thestrong, interconnected carcass.

The barrier layer 806 is immediately adjacent the carcass 802. Thebarrier layer is formed of the polyarylene sulfide composition andprovides strength and flexibility while preventing permeation of thefluid carried by the riser through the riser wall. In addition, thebarrier layer 806 formed of the polyarylene sulfide composition canresist degradation by both the fluid carried by the riser (e.g., theproduction fluid, the injection fluid, etc.) as well as by temperatureconditions under which the riser is utilized. The barrier layer 806 cangenerally be between about 3 and about 10 millimeters in thickness andcan be extruded from a melt over the carcass 2.

The riser 800 will also include an outer layer 822 that provides anexternal sleeve and an external fluid barrier as well as providingprotection to the riser from external damage due to, e.g., abrasion orencounters with environmental materials. The outer layer 822 can beformed of a polymeric material such as the polyarylene sulfidecomposition or a high density polyethylene that can resist bothmechanical damage and intrusion of seawater to the inner layers of theriser. According to one embodiment, the outer layer 822 can be acomposite material that includes a polymeric material in conjunctionwith a reinforcement material such as carbon fibers, carbon steelfibers, or glass fibers.

A hoop strength layer 804 can be located external to the barrier layerto increase the ability of the riser to withstand hoop stresses causedby forced applied to the riser wall by a pressure differential. The hoopstrength layer can generally be a metal layer formed of, e.g., ahelically wound strip of carbon steel that can form a layer of fromabout 3 to about 7 millimeters in thickness. The hoop strength layer canresist both internal pressure and bending of the riser. In oneembodiment, the carbon steel strip that forms the hoop strength layer804 can define an interlocking profile, for instance an S- orZ-cross-sectional configuration, such that adjacent windings interlockwith one another to form a stronger layer. In one embodiment, the hoopstrength layer can include multiple materials for added strength. Forexample, in an embodiment in which design and pressure requirements callfor higher burst strengths, a second flat metal strip can be helicallywound over the interlocked metal strips of the hoop strength layer toprovide additional strength for this layer. An intervening polymericlayer such as an anti-wear layer discussed further herein can optionallybe located between the two layers of the hoop strength layer as well.

Additional strength layers 818 and 820 can be formed of helically-woundmetal (generally carbon steel) strips. The strength layers 818 and 820can be separated from the hoop strength layer 804 and from each other bypolymeric anti-wear layers 817 and 819. The strength layers 818 and 820can provide additional hoop strength as well as axial strength to theriser. Though the riser 800 includes two strength layers 818, 820, itshould be understood that a riser may include any suitable number ofstrength layers, including no strength layers, one, two, three, or morestrength layers. In general, the helically wound metal strips ofstrength layers 818 and 820 will overlap but need not interlock. Assuch, the strength layers 818, 820 may have a width of from about 1millimeter to about 5 millimeters.

The intervening anti-wear layers 817, 819 can be formed of thepolyarylene sulfide composition or alternatively can be formed of otherpolymers such as a polyamide, a high density polyethylene, or the like.In one embodiment, the anti-wear layers 817, 819 can be a compositematerial that includes unidirectional fibers, for instance carbon orglass fibers. For instance, the anti-wear layers 817, 819 can be formedof a polymer tape or fiber-reinforced polymer tape such as a pultrudedpolymer tape or ribbon that is helically wound over each strength layer.The anti-wear layers 817, 819 can prevent wear of the adjacent strengthlayers that can come about due to motion of the strips forming thelayers. The anti-wear layers 817, 819 can also prevent birdcaging of theadjacent layers. As with the strength layers 818, 820 of the riser 800,the number of anti-wear layers is not particularly limited, and a risercan include no anti-wear layers, one anti-wear layers, or multipleanti-wear layers depending upon the depth and local environment in whichthe riser will be utilized, the fluid to be carried by the riser, and soforth. The anti-wear layers 817, 819, can be relatively thin, forinstance between about 0.2 and about 1.5 millimeters.

A riser may include additional layers as are generally known in the art.For example, a riser may include an insulation layer, for instanceimmediately internal to the outer layer 822. An insulation layer, whenpresent can be formed of a foam, fibrous mat, or any other insulationmaterial as is known. By way of example, single or multiple layers of aninsulation tape can be wound onto the outer strength layer to form aninsulation layer between the outer strength layer 820 and the outerlayer 822.

While the above description is for an unbounded flexible riser, itshould be understood that the polyarylene sulfide composition maylikewise be utilized in forming a bonded flowline. For example, thepolyarylene sulfide composition may be utilized in forming a barrierlayer and optionally one or more additional layers of a bonded flowlinefor use in an offshore oil and gas facility.

Other flowlines for use in an oil and gas facility, for instancejumpers, pipelines, fluid supply lines, etc., can have the same generalconstruction as a riser 800 as illustrated in FIG. 8, or may varysomewhat as to particular layers include in the multilayer flowline. Forexample, an injection fluid supply line, which supplies injection fluidsuch as methanol, glycol, and/or water to a well head, need not meet thesame performance specifications as a production riser. Accordingly, atleast a portion of this flowline need not include all of the variousstrength-enhancing layers as the riser described above. For instance,flowlines as described herein can include the barrier layer formed ofthe polyarylene sulfide composition as the innermost layer, in thoseembodiments in which the flowline specifications do not call for aninner carcass layer as the riser described above.

The diameters of flowlines can also vary widely as is known in the art.For instance, a production fluid riser can generally have a relativelylarge inner diameter, from about 5 centimeters (about 2 inches) up toabout 60 centimeters (about 24 inches) or even greater in someembodiments, while flowlines that carry supporting fluids to or from thewell head, the manifold, the storage facility, etc., can be larger orsmaller than the production fluid flowlines. For instance, an injectionfluid flowline can be smaller than a production fluid flowline, forexample, between about 5 centimeters (2 inches) to about 15 centimeters(6 inches) in inner diameter.

A flowline design can vary over the length of the flowline. Forinstance, as the offshore flowlines reach greater depths, extend togreater offshore distances, and operate at higher pressures, theflowlines that supply supporting fluids to the wells, manifolds, etc.that directly or indirectly support the hydrocarbon product extractioncan increase in complexity. Accordingly, the supporting fluids may besupplied to the equipment using flowlines that vary along their lengthfrom a flowline that is designed for, e.g., lower pressure operation toa flowline that includes additional reinforcement layers for use in amore extreme environment. As the working pressure of the systemincreases, the supply pressures and injection pressures also increase.This increase in supply pressure may require that the flowlineassemblies also be reinforced and re-engineered around the higherpressures at those locations of the system. Thus, the flowlines may varyin design across the entire length of the line. In any case, at least aportion of the flowlines can include a barrier layer formed of thepolyarylene sulfide composition.

Flowlines can also be bundled. By way of example, FIG. 9 illustrates abundled riser 129. The outer casing 128 can be, e.g., a steel casing ora composite casing including multiple polymeric and/or metal layers. Thebundled riser 129 includes two production fluid risers 130 that cancarry hydrocarbon production fluid from the sea floor to a surfacefacility. The production fluid risers 130 can be multilayer risers asdescribed above and including a barrier layer formed of the polyarylenesulfide composition. The bundled riser 129 also includes a hydraulicsupply flowline 132 that supplies hydraulic fluid to the operatingdevices located upon the sea floor and an injection fluid flowline 133.The bundled riser 129 includes an annulus line 131, which communicateswith the interspaces 127 within the bundled riser 129 and may be used toestablish circulation through the production flowlines and theinterspaces (or annulus). For instance, a lower end of the annulus line131 may be connected to a port such as a side port for communicationwith the interspaces 127. One or more valves can be mounted between thelower end of the annulus line 131 and the interspaces 127 forcontrolling fluid flow between the annulus line 131 and the interspaces.The bundled riser 129 can also include a control cable 134 that can beused to control the operation of devices located upon any wellheadaccording to standard practice as is known to the art.

A bundled riser can include two production fluid risers 130 asillustrated in FIG. 9 or can alternatively carry a single productionfluid riser or more than two production fluid risers. For instance, abundled riser can include a plurality of production fluid risersarranged around a centrally extending conduit or tube all of which canbe surrounded by external casing. For example, the production fluidrisers can border on each other and form a ring and also bear againstthe inner side of the external casing and against the outer side of theinner conduit, which can improve stability of the bundled riser withoutaffecting flexibility. The inner tube can carry additional flowlines,such as a hydraulic flowline, injection fluid flowline, etc. asdescribed. In another embodiment, the inner tube can function as abuoyancy line to supply additional buoyancy to the riser. In yet anotherembodiment, additional flowlines may be located in the interspacesbetween the production fluid risers and external to the inner tube.

FIG. 10A and FIG. 10B illustrate a pipe-in-pipe arrangement 140 in aside view (FIG. 10A) and a cross sectional view (FIG. 10B) in which oneor all of the walls of the lines 148, 141, and 142 can include a barrierlayer formed of the polyarylene sulfide composition. In this particularembodiment, the pipe-in-pipe flowline is an insulated flowline thatincludes an inner production fluid flowline 142 encased in an externalcasing 148. The inner production fluid flowline 142 is also encased in ajacket 141. In this particular embodiment, the annulus 143 between theinner production fluid flowline 142 and the jacket 141 is filled with aninsulation material 144, such as an open celled foam as is known in theart. The space 145 external to the jacket 141 and inside the externalcasing 140 can carry a supporting fluid, such as water, methanol, etc.or can be filled with a high pressure gas, which can further improve theinsulative properties of the pipe-in-pipe flowline, for instance byproviding access points 146 from the space 145 that carries the highpressure gas to the insulation material 144. The pipe-in-pipearrangement can also include spacers 147 to maintain the desireddistances between the production fluid flowline 142, the jacket 142, andthe external casing 148. Other combination flowlines such as piggy-backflowlines are also encompassed herein.

The polyarylene sulfide composition may be utilized in forming allmanner of components as may be incorporated in a fluid handling systemin addition to pipes and hoses such as, without limitation, flanges,valves, valve seats, seals, sensor housings, thermostats, thermostathousings, diverters, linings, propellers, and so forth. In oneembodiment, the polyarylene sulfide composition may be utilized inautomotive applications, for instance in hoses, belts, etc. that may besubject to extreme temperatures as well as large temperaturefluctuations during use.

The polyarylene sulfide composition may be used to form single- ormultilayered containers including bags, bottles, storage tanks and othercontainers such as may be produced by extrusion, extrusion blow molding,injection blow molding, stretch blow molding, or other conventionalprocesses for forming such articles.

The polyarylene sulfide composition can also be beneficially utilized informing films, fibers and fibrous products. For example, extrusionprocesses as are known in the art can be utilized in forming films orfibers of the polyarylene sulfide composition.

Fibers can include, without limitation, staple, continuous,multifilament, or monofilament fibers as may be formed usingconventional melt spinning equipment. By way of example, FIG. 11illustrates a process and system 410 by which a drawn fiber may beformed of the polyarylene sulfide composition. According to theillustrated embodiment, the previously formed polyarylene sulfidecomposition, for instance in the form of pellets or chips, can beprovided to an extruder apparatus 412. The extruder apparatus 412 caninclude a mixing manifold 411 in which the polyarylene composition canbe heated to form a molten composition and optionally mixed with anyadditional additives. If desired, to help ensure the fluid state of themolten mixture, the molten mixture can be filtered prior to extrusion.For example, the molten mixture can be filtered to remove any fineparticles from the mixture by use of a filter with about 325 mesh orfiner.

Following formation of the molten mixture, the mixture can be conveyedunder pressure to the spinneret 414 of the extruder apparatus 412, whereit can be extruded through multiple spinneret orifices to form one ormore fibers or filaments 409. Extrusion temperatures in the range ofabout 280° C. to about 340° C. can be employed, for instance in therange of about 290° C. to about 320° C. Following extrusion of thepolyarylene sulfide composition to form the fibers or filaments, theundrawn fibers or filaments 409 can be quenched in a liquid bath 416 andcollected by a take-up roll 418, for instance to form a multifilamentfiber structure or fiber bundle 428. Take-up roll 418 and roll 420 canbe within bath 416 and convey individual fibers or filaments 409 and thegathered fiber bundle 428 through the bath 416. Dwell time of thematerial in the bath 416 can vary, depending upon line speed, bathtemperature, fiber size, etc. Following exit from the quenching bath,the fiber bundle 428 can pass through a series of nip rolls 423, 424,425, 426 to remove excess liquid from the fiber bundle 428. Optionally,a lubricant can be applied to the fiber bundle 428. For example, a spinfinish can be applied at a spin finish applicator chest 422. Following,the polyarylene sulfide fiber bundle can be drawn at temperatures in therange of 90° C. to 110° C. using conventional equipment having a drawzone designed to heat the fiber to the appropriate temperature. Forexample, in the embodiment illustrated in FIG. 11, the fiber bundle 428can be drawn in an oven 443. Additionally, in this embodiment, the drawrolls 432, 434 can be either interior or exterior to the oven 443, as isgenerally known in the art. Subsequent to drawing the fiber bundle 428 ahot roll 440 or heated zone in a temperature range of 100° C. to about200° C. can be used to at least partially crystallize the formedpolyarylene sulfide fiber 430.

According to another embodiment, melt-blown fibers can be formed of thepolyarylene sulfide composition. FIG. 12 illustrates one embodiment of amelt-blowing process as may be utilized. The melt-blowing processincludes extruding the polyarylene sulfide composition from an extruder527 through a linear array of single-extrusion orifices 528 directlyinto a high velocity heated air stream defined generally between 530 aand 530 b. The rapidly moving hot air greatly attenuates the fibers 529as they leave the orifices 528. The die tip is designed in such a waythat the holes are in a straight line with high velocity air impingingfrom each side 530 a, 530 b. A typical die will have 10-20 mil(0.25-0.51 mm) diameter holes spaced at 20 to 50 per inch. The impinginghigh-velocity hot air attenuates the filaments and forms the desiredmicrofibers. Typical air conditions range from about 200° C. to about370° C. Immediately around the die, a large amount of ambient air isdrawn into the hot air stream containing the fibers. The ambient aircools the hot gas and solidifies the fibers.

The discontinuous fibers may be deposited on a conveyor or takeup screen521 fed through rolls 525, 526 to form a random, entangled web. Thefibers can be directed to the conveyor 521 by use of a suction device531 that utilizes, e.g., a fan 533 that draws air away via tubing 532.Under the proper conditions, the fibers can still be somewhat soft atlaydown and will tend to form fiber-fiber bonds—that is, they will sticktogether. The combination of fiber entanglement and fiber-to-fibercohesion generally produces enough entanglement so that the web can behandled without further bonding. The web may also be deposited onto aconventional spun but not bonded web to which the former is thenthermally bonded.

Fibers formed of the polyarylene sulfide composition can be utilized ina variety of fibrous substrates for a variety of applications including,without limitation, as battery separators, oil absorbers, filter media,hospital-medical products, insulation batting, and the like. By way ofexample, FIG. 13 illustrates a fibrous mat 612 comprising a plurality ofpolyarylene sulfide melt-blown fibers 614 as may be used to capture fineparticles from a gas or liquid stream. For instance, a filter includingfibers formed of the polyarylene sulfide composition can be utilized infiltering fuel, oil, exhaust, other fluids in an engine, e.g., anautomotive engine, or in forming a filter bag, for instance as may beutilized with an industrial smokestack. Fibers formed of the polyarylenesulfide composition can also be utilized in forming insulationmaterials, such as insulative paper or fabrics in electrical components.

Still further, the composition may be employed in completely differentenvironments, such as an electronic component such as a wire, a cable,or an umbilical. For example, and as illustrated in FIGS. 14A and 14B,the polyarylene sulfide composition can be utilized to form sheathing701 around a wire 703 or sheathing 702 around a cable 704 for protectionand encasement purposes. For instance, the polyarylene sulfidecomposition can be extruded by use of a sheathing machine around a wireor cable to form the protecting coating on the external surface of thewire/cable.

In another embodiment the polyarylene sulfide composition can be used informing devices for use in conjunction with cables, such as a cableharness or a cable wrap (also commonly referred to as a tie wrap). Forexample, one or more portions of a cable harness as may be utilized in avehicle or other types of machinery can be formed from the polyarylenesulfide composition. For example, FIG. 15 illustrates a cable harness asmay incorporate the polyarylene sulfide composition. Referring to FIG.15 a cable harness 1100 includes a wire group 1102 formed of a pluralityelectric wires. Connector terminals 1103 are at both ends of the wiregroup 1102. A braid sleeve 1104 is provided around an outer periphery ofthe wire group 1102.

The braid sleeve 1104 can be formed by braiding a plurality ofmetallized fibers that can be formed by plating a fiber formed of thepolyarylene sulfide composition with a metal such as, e.g., aluminum,copper, or alloy thereof. The braid sleeve 1104 can be wrapped by anadhesive tape 1106 at the ends and fixed to the wire group 1102, so asto prevent the braid sleeve 4 from raveling. At each end 1106 of thebraid sleeve 1104, an extension 1107 of the metallized fiber used toform the braid sleeve 1104 can be included. The extensions 1107 canallow grounding of the cable harness. The cable harness also includesground connecting parts 1105, in which both ends of the braid sleeve1104 and both ends of an outer conductor in the wire group 1102 areelectrically connected in parallel. Of course, any cable harness as isgenerally known in the art may incorporate the polyarylene sulfidecomposition.

The polyarylene sulfide composition can be utilized to form a variety ofelectronic components that may employ a molded part such as, forinstance, cellular telephones, small portable computers (e.g.,ultraportable computers, netbook computers, and tablet computers),wrist-watch devices, pendant devices, headphone and earpiece devices,media players with wireless communications capabilities, handheldcomputers (also sometimes called personal digital assistants), remotecontrollers, global positioning system (GPS) devices, handheld gamingdevices, battery covers, speakers, camera modules, integrated circuits(e.g., SIM cards), etc.

In one embodiment, the polyarylene sulfide composition can be used toform components for vehicles. For instance, the polyarylene sulfidecomposition can be used to form components for heavy trucks (i.e.,vehicles having a gross vehicle weight range of over about 9000 kg(about 19,800 pounds)). Heavy trucks face unique operating conditionsdue to the nature of both the vehicles themselves as well as the natureof the use of the vehicles. For instance, the engines must often operateat high temperatures, particularly when carrying a load, and thevehicles will often encounter large mechanical stress and environmentalassaults during use. The excellent strength and flexibilitycharacteristics of the polyarylene sulfide can provide heavy truckcomponents that are better able to withstand the operating conditions ofthese vehicles. Heavy duty trucks can include trucks having two, three,four, or more axles and can include both tractors and trailers that maybe pulled by tractors. By way of example, contractor's trucks, deliverytrucks, dump trucks, panel trucks, mix-in-transit trucks, trucktractors, and so forth can include components formed of the polyarylenesulfide composition.

Heavy truck components as may be formed of the polyarylene sulfidecomposition can include, without limitation, hoses, belts, fuel lines,cooling system components, brake components, couplings, etc. Forexample, the polyarylene sulfide composition can be beneficiallyutilized in urea tanks of heavy duty trucks. FIGS. 16A and 16Bschematically depict a urea tank 310 that includes a container 312 witha bottom wall 314 and a top wall 316. In the top wall 316 there is anopening 318 for the accommodation of a set of fittings 330. Thecontainer 312 further comprises a filling opening 317. The set offittings 330 comprises a head 332 arranged to be connected fluid-tightlyto the opening 318 in the top wall 316. This may be achieved in manydifferent ways, e.g. by a flange connection between a radial flange 320(FIG. 16B) of the opening 318 and a radial flange 334 of the head 332.The head 332 may also take the form of a screw cap with internal orexternal threads adapted to engage with complementary threads (notdepicted) of the opening 318. A multiplicity of fittings 336 extend fromthe head 332 into the container 312. The fittings 336 may include asuction pipe for urea/water solution, a return pipe for unconsumedsolution, a heating coil for thawing the solution when the latter isfrozen by low ambient temperature, and a level sensor for the solutionin the container. Beneficially, one or more of the suction pipe, thereturn pipe and the heating coil and/or a protective cover 340 may beformed of the polyarylene sulfide composition.

The excellent strength characteristics of the polyarylene sulfidecomposition can protect the components of the fittings 336 from harmfulmechanical effects due to icing in the container 312, and theflexibility of the polyarylene sulfide composition allows the fittings336 to sustain affects from movements of ice in the container 312.

Another exemplary urea tank assembly 1410 is shown in FIG. 17. The ureatank assembly includes a reservoir 1412 having a cavity 1414 configuredfor receiving and holding a liquid, such as urea solution 1416. Theassembly further includes a tubular member 1418 that can be formed ofthe polyarylene sulfide composition having a one or more, or pluralityof, openings 1420 formed therethrough for providing fluid communicationbetween a hollow portion 1422 of the hollow member and the cavity of thereservoir. The assembly further includes a heater 1424 located proximateto or formed by the hollow portion to heat the urea solution within andabout the hollow member. The assembly also includes a pump 1426 forcausing fluid from within the cavity 1414, and in some exemplaryembodiments from within the hollow portion, to be pumped to an exhaustgas stream for dispensing therein.

In operation, the urea solution 1416 is pumped, injected or otherwiseplaced into the cavity 1414 through suitable urea input conduit 1428 orthrough other means such as a capped opening 1450. The urea solution isheated through heater 1424 and pumped through a urea outlet conduit 1430through pump 1426. Optionally, pumping of the urea solution may beachieved through a fluid level switch 1432, 1456 and heating may bebased upon temperature reading from a temperature sensor 1434. The ureasolution travels along the urea outlet conduit to a port in fluidcommunication with an exhaust gas conduit from an engine. The portprovides means, such as an injector, for delivery into an exhaust gasstream and more particularly upstream from an exhaust gas treatmentdevice.

Heavy truck components as may be formed from the polyarylene sulfidecomposition are not limited to urea tanks. For instance, tubular membersas described above can be designed for heavy truck use in a fluidtransport system including a hose assembly or a fuel line assembly. Forinstance, a multi-layer tubular component can be formed that includes asan inner layer the polyarylene sulfide composition that can withstandthe fluids and environmental conditions expected within the member. Abarrier layer can be adjacent to the inner layer and may be formed of amaterial that can exhibit low permeability to materials to be carried bythe tubular member, e.g., diesel fuel. For example, the barrier layermay be formed of a polyamide such as PA6, PA11, PA12, PA66, PA 610,PA46, etc., as well as blends of polymers.

A multi-layer tubular member can include a tie layer that can facilitatebonding between adjacent layers. A tie layer may include a rubbercomposition based on, e.g., epichlorohydrin rubber, nitrile rubber,butadiene rubber/poly(vinyl chloride) blends, hydrogenated nitrilerubber, thermoplastic elastomers, or the like. The tie layer could be anadhesive coating as discussed above.

A multi-layer tubular member for use in heavy truck applications mayinclude a cover that can be made of one or more suitable flexibleelastomeric or plastic materials designed to withstand the exteriorenvironment encountered. For instance, the cover may be formed of apolyarylene sulfide composition that is the same or different as thepolyarylene sulfide composition utilized in forming the inner tube.According to another embodiment, the outer cover can be based on arubber formulation such as, without limitation, hydrogenated nitrilerubber, chlorosulfonated polyethylene, polychloroprene, epichlorohydrinrubber, ethylene/vinylacetate copolymers, polyacrylic rubber, ethylenealkene copolymer, butadiene rubber/poly(vinyl chloride) blends,chlorinated polyethylene, and the like, which may be formulated withother ingredients in accordance with known methods of rubbercompounding. A reinforcement layer as well as additional intermediatelayers as discussed above may also be present in a multilayer tubularmember.

A tubular member including the polyarylene sulfide composition canexhibit excellent flexibility and heat resistance, which can be ofbenefit if forming a tubular member for the charge air system of a heavyduty truck. A heat resistant tubular member for use in the air handlingsystem can include an inner layer that includes the polyarylene sulfidecomposition and an outer layer formed on an outer peripheral surface ofthe tubular inner layer that can include a flame retardant. For example,the outer layer can be formed by using a material containing non-halogenflame retardant.

A charge air system coupling can be formed of the polyarylene sulfidecomposition that can provide a connection between various chargecomponents of the charge air system including, without limitation, atthe compressor inlet and discharge, at the charge air cooler, and/or atthe turbine inlet and discharge. The flexibility and strength of thepolyarylene sulfide composition can provide for a charge air systemcoupling that can handle slight misalignments between components of thesystem as well as isolate vibration between ends of the coupling. Inaddition, the resistance characteristics of the polyarylene sulfidecomposition can improve the coupling with regard to ozone resistance andincrease the life of the component.

The polyarylene sulfide composition may also be beneficially utilized informing components of an exhaust system for venting exhaust from anexhaust manifold of a diesel engine. A typical exhaust system caninclude an exhaust line and all or a portion of the exhaust line can beformed of the polyarylene sulfide composition.

The air brake system of a heavy duty truck may also include componentsformed of the polyarylene sulfide composition. For example, a coiled airbrake hose assembly can include a coiled hose that may be a single layerhose or a multi-layer hose as described above in which at least onelayer includes the polyarylene sulfide composition.

Components of other vehicles can be formed of the polyarylene sulfidecomposition, in addition to heavy duty trucks. For example, automotivefuel lines for use in cars or trucks of any size can be formed of thepolyarylene sulfide composition. The polyarylene sulfide composition canbe processed according to standard formation techniques to form a fuelline that can be either a single layer fuel tube or a multi-layer fuelhose. Fuel lines as encompassed herein are tubular shaped members havinga hollow passage therethrough that allows passage of a fluid, a liquid,a gas, or a mixture thereof, through the fuel line. By way of example,FIG. 18 illustrates a portion of the fuel system that can include a fuelline that includes the polyarylene sulfide composition. FIG. 18illustrates the intake portion generally 1 of a fuel system and includesa fuel filler neck 42, a filler tube 44, a fuel tank 48, a vent tube 46,and a gas cap 44, and is supported by an automobile body 46, whichincludes a movable cover 40 to conceal the gas cap 44. The filler neck42 generally includes a funnel-shaped member 48. The filler neck 42 mayreceive a nozzle receptor 52, which is an insert adapted to receive afuel nozzle 56 during fueling. The member 48 is defined at one end by aninlet opening 50 adapted to receive the gas cap 44, which screwsdirectly into threads integrally formed in the member 48.

An opposite end of the member 48 is defined by an outlet opening 53,which is coupled to a first end 54 of a fuel line 44. The fuel line 44can be a single layer tube or a multi-layer hose formed of thepolyarylene sulfide composition. At a second end 55, the fuel line 44 iscoupled to the fuel tank 48. The fuel tank system may also include avent line 46 that connects to the member 48 at funnel vent opening 57and to the fuel tank 48 at fuel tank opening 58. The vent line 46 allowsdisplaced vapors in the fuel tank 48 to be vented during fueling. Thevent line 46 may also be a single layer tube or a multi-layer hose thatcan be formed from the polyarylene sulfide composition.

Any fuel line that has a generally tubular shape and includes a hollowpassage through the line (i.e., in the axial direction of the tubularmember) as may be included in a vehicle engine, including both gasolineand diesel engines, may include one or more layers formed of thepolyarylene sulfide composition, and it should be understood that thefuel lines are not in any way limited to the in-take portion of the fuelsystem as illustrated in FIG. 18. For example, fuel lines encompassedherein include fuel feed lines that carry fuel from the fuel tank to theengine and can be located downstream and/or upstream of the fuel filter.Other fuel lines as may incorporate the polyarylene sulfide compositioncan include, without limitation, fuel return lines, fuel bypass lines,fuel crossover lines, breather lines, evaporation lines, etc.

A fuel line in the form of a single layer tube can be utilized, forexample, in forming a vent line 46 and/or a fuel line 44 as illustratedin FIG. 18. A single layer tube fuel line can generally have a wallthickness of less than about 3 millimeters, for instance from about 0.5to about 2.5 millimeters, or from about 0.8 to about 2 millimeters.Single layer tube fuel lines can generally have a cross sectionaldiameter of less than about 10 millimeters, or less than about 5millimeters in one embodiment. The length of a single layer tube fuelline can vary depending on the specific application and can berelatively long, for instance about 1 meter long or more, or can beshort, for instance less than about 50 centimeters, or less than about10 centimeters. Additionally, a single layer tube 50 can have acorrugated surface or a smooth surface.

A fuel line that incorporates the polyarylene sulfide composition can bea multi-layered tubular member that incorporates the polyarylene sulfidecomposition in one or more layers of the fuel line. Multi-layer fuellines can include two, three, or more layers, as is known. Multi-layerfuel lines, similar to single layer fuel tubes, can be formed to have awide variety of cross sectional and length dimensions, as is known inthe art. In general, each layer of a multi-layer fuel line can have awall thickness of less than about 2 millimeters, or less than about 1millimeter; and the inner diameter of the multi-layer fuel line cangenerally be less than about 100 millimeters, less than about 50millimeters, or less than about 30 millimeters.

The excellent barrier properties of the polyarylene sulfide compositioncombined with the chemical resistance properties of the polyarylenesulfide composition make it suitable for use in forming an inner layerof a multi-layer fuel line. However, the polyarylene sulfide compositionis not limited to utilization as an inner layer of a multi-layer fuelline. The high strength characteristics of the polyarylene sulfidecomposition combined with the excellent barrier properties and goodflexibility make the composition suitable for use in forming outerlayers and/or intermediate layers of a multi-layer fuel line in additionto or alternative to forming the inner layer of the multi-layer fuelline.

Additional layers can be formed of a material that is the same ordifferent than the polyarylene sulfide composition that forms the innerlayer. For example, intermediate layers, outer layer, and adhesivelayers of a fuel line can be formed of materials as described above fortubular members as may be formed of the polyarylene sulfide composition.

Vehicle components as may be formed from the polyarylene sulfidecomposition can include components that can be formed according to ablow molding process, such as those described above. By way of example,the fuel filler neck 42 and/or the gasoline tank 48 as illustrated inFIG. 18 can be formed from the polyarylene sulfide composition accordingto a blow molding process. Blow molded components such as a gasolinetank or other reservoirs (e.g., expansion tanks, fluid containers, etc.)can be single layer or multi-layered components. Components of theventilation system such as air ducts can be formed of the polyarylenesulfide composition according to a blow molding process as can manyother components including, without limitation, support structures,running boards, struts, grill guards, pillars, flooring, etc.

In another embodiment, the polyarylene sulfide composition may beutilized in aeronautical applications. By way of example, FIG. 19illustrates one embodiment in which the polyarylene sulfide compositioncan be utilized in aircraft interior, for instance in forming panelswithin an aircraft interior. FIG. 19 schematically illustrates across-section through an aircraft fuselage 850 of the single aisle type,though the polyarylene sulfide composition may be beneficially utilizedin forming aircraft of any size and shape. Panels as may be formed ofthe polyarylene sulfide composition can include, by way of example, andwithout limitation, the overhead racks or storage bins 852, theover-aisle head panels 854 that widen upwardly to an enlarged ceilingpanel area, a ceiling panel 856, side wall panels 858, and lower wallpanels 855. The number and size of the individual panels will generallyvary from one aircraft to another. For example, a typical cross-sectionof the type of aircraft having fuselage 850 includes two storage bins,one ceiling panel, two side wall panels, and two lower wall panels.Variations of individual components are well known in the art. Ofcourse, the polyarylene sulfide composition may be utilized in formingother components of an aircraft such as fuel lines as described above,components of the ventilation system as described, and so forth.

Embodiments of the present disclosure are illustrated by the followingexamples that are merely for the purpose of illustration of embodimentsand are not to be regarded as limiting the scope of the invention or themanner in which it may be practiced. Unless specifically indicatedotherwise, parts and percentages are given by weight.

Formation and Test Methods

Injection Molding Process:

Tensile bars are injection molded to ISO 527-1 specifications accordingto standard ISO conditions.

Melt Viscosity:

All materials are dried for 1.5 hours at 150° C. under vacuum prior totesting. The melt viscosity is measured on a capillary rheometer at 316°C. and 400 sec⁻¹ with the viscosity measurement taken after five minutesof constant shear.

Tensile Properties:

Tensile properties including tensile modulus, yield stress, yieldstrain, strength at break, elongation at yield, elongation at break,etc. are tested according to ISO Test No. 527 (technically equivalent toASTM D638). Modulus, strain, and strength measurements are made on thesame test strip sample having a length of 80 mm, thickness of 10 mm, andwidth of 4 mm. The testing temperature is 23° C., and the testing speedsare 5 or 50 mm/min.

Flexural Properties:

Flexural properties including flexural strength and flexural modulus aretested according to ISO Test No. 178 (technically equivalent to ASTMD790). This test is performed on a 64 mm support span. Tests are run onthe center portions of uncut ISO 3167 multi-purpose bars. The testingtemperature is 23° C. and the testing speed is 2 mm/min.

Deflection Temperature Under Load (“DTUL”):

The deflection under load temperature was determined in accordance withISO Test No. 75-2 (technically equivalent to ASTM D648-07). Moreparticularly, a test strip sample having a length of 80 mm, thickness of10 mm, and width of 4 mm was subjected to an edgewise three-pointbending test in which the specified load (maximum outer fibers stress)was 1.8 Megapascals. The specimen was lowered into a silicone oil bathwhere the temperature is raised at 2° C. per minute until it deflects0.25 mm (0.32 mm for ISO Test No. 75-2).

Notched Charpy Impact Strength:

Notched Charpy properties are tested according to ISO Test No. ISO179-1) (technically equivalent to ASTM D256, Method B). This test is runusing a Type A notch (0.25 mm base radius) and Type 1 specimen size(length of 80 mm, width of 10 mm, and thickness of 4 mm). Specimens arecut from the center of a multi-purpose bar using a single tooth millingmachine. The testing temperature is 23° C., −30° F., or −40° F. asreported below.

Unnotched Charpy Impact Strength:

Unnotched Charpy properties are tested according to ISO Test No. 180(technically equivalent to ASTM D256). The test is run using a Type 1specimen (length of 80 mm, width of 10 mm and thickness of 4 mm).Specimens are cut from the center of a multi-purpose bare using a singletooth milling machine. The testing temperature is 23° C.

Izod Notched Impact Strength:

Notched Izod properties are tested according to ISO Test No. 180(technically equivalent to ASTM D256, Method A). This test is run usinga Type A notch. Specimens are cut from the center of a multi-purpose barusing a single tooth milling machine. The testing temperature is 23° C.

Density and Specific Gravity:

Density was determined according to ISO Test No. 1183 (technicallyequivalent to ASTM D792). The specimen was weighed in air then weighedwhen immersed in distilled water at 23° C. using a sinker and wire tohold the specimen completely submerged as required.

Vicat Softening Temperature:

Vicat Softening temperature was determined according to method A, with aload of 10 N and according to method B with a load of 50 N as describedin ISO Test No. 306 (technically equivalent to ASTM D1525), both ofwhich utilized a heating rate of 50 K/h.

Water absorption was determined according to ISO Test No. 62. The testspecimens are immersed in distilled water at 23° C. until the waterabsorption essentially ceases (23° C./sat).

Complex Viscosity:

Complex viscosity is determined by a Low shear sweep (ARES) utilizing anARES-G2 (TA Instruments) testing machine equipped with 25 mm SS parallelplates and using TRIOS software. A dynamic strain sweep was performed ona pellet sample prior to the frequency sweep, in order to find LVEregime and optimized testing condition. The strain sweep was done from0.1% to 100%, at a frequency 6.28 rad/s. The dynamic frequency sweep foreach sample was obtained from 500 to 0.1 rad/s, with strain amplitude of3%. The gap distance was kept at 1.5 mm for pellet samples. Thetemperature was set at 310° C. for all samples.

Melt strength and melt elongation is performed on ARES-G2 equipped EVFfixture. The flame bar sample was cut as shown in FIG. 20. The same areaof flame bar was used for each run, in order to keep the crystallinityof test sample same and thus to minimize the variation betweenreplicates. A transient strain was applied to each sample at 0.2/s rate.At least triplicate run was done for each sample to obtain arepresentative curve.

Permeation Resistance:

The fuel permeation studies were performed on samples according to SAETesting Method No. J2665. For all samples, stainless-steel cups wereused. Injection molded plaques with a diameter of 3 inches (7.6centimeters) were utilized as test samples. The thickness of each samplewas measured in 6 different areas. An O-ring Viton® fluoroelastomer wasused as a lower gasket between cup flange and sample (Purchased fromMcMaster-Carr, cat#9464K57, A75). A flat Viton® fluoroelastomer(Purchased from McMaster-Carr, cat#86075K52, 1/16″ thickness, A 75) wasdie-cut to 3 inch (7.6 cm) OD and 2.5 inch (6.35 cm) ID, and used as theupper gasket between the sample and the metal screen. The fuel, about200 ml, was poured into the cup, the cup apparatus was assembled, andthe lid was finger-tightened. This was incubated in a 40° C. oven for 1hour, until the vapor pressure equilibrated and the lid was tightened toa torque 15 in-lb. The fuel loss was monitored gravimetrically, dailyfor the first 2 weeks followed by twice a week for the rest of thetesting period. A blank run was done in the same manner with an aluminumdisk (7.6 cm diameter, 1.5 mm thickness) and the result was subtractedfrom the samples. All samples were measured in duplicate. The normalizedpermeation rate was calculated following an equilibration period. Thepermeation rate for each sample was obtained from the slope of linearregression fitting of daily weight loss (gm/day). The normalizedpermeation rate was calculated by dividing the permeation rate by theeffective permeation area and multiplying by average thickness ofspecimen. The average permeation rates are reported.

Salt Resistance:

For testing resistance to zinc chloride, tensile bar samples wereimmersed in a 50% aqueous solution (by weight) of zinc chloride for 200hours at 23±2° C. Following the samples were tested for Charpy notchedimpact strength as described at −30° C.

For testing resistance to calcium chloride, tensile bar samples wereimmersed in a 50% aqueous solution (by weight) of calcium chloride for200 hours at 60±2° C. and held for an additional 200 hours out ofsolution at 60±2° C. Following, the samples were tested for Charpynotched impact strength as described at −30° C.

Hydrocarbon Volume Uptake:

Absorption and diffusion testing was performed using the tab ends cutfrom supplied tensile bars. Each material was immersed in Brent crudeoil, hydrocarbon/water mixture (and in a one-off test to hydrocarbononly). Rates and amounts of liquid absorbed were measured. Thehydrocarbon liquid mixture had the following composition:

Volume percent (%) Composition 10 Distilled water 60 70% heptane, 20%cyclohexane and 10% Toluene balance Nitrogen

All exposure testing was conducted at 130° C. for a period of two weeksutilizing an air-circulating oven, air having been removed from the testvessel by purging with nitrogen; the test being conducted at vaporpressure.

Example 1

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfideavailable from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene andglycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Disulfide: 2,2-dithiodibenzoic acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the disulfide was fed usinga gravimetric feeder at barrel 6. Materials were further mixed thenextruded through a strand die. The strands were water-quenched in a bathto solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 1, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 1 Component Addition Point Sample 1 Sample 2 Lubricant main feed0.3 0.3 Disulfide barrel 6 1.0 Impact Modifier main feed 25.0 25.0Polyarylene Sulfide main feed 74.7 73.7 Total 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 2, below.

TABLE 2 Sample 1 Sample 2 Melt Viscosity (poise) 3328 4119 TensileModulus (MPa) 1826 1691 Tensile Break Stress (MPa) 43.73 44.98 TensileBreak Strain (%) 96.37 135.12 Std. Dev. 39.07 34.40 Notched CharpyImpact 61.03 53.00 Strength at 23° C. (kJ/m²)

Samples were annealed at 230° C. for 2 hours and re-tested for physicalcharacteristics. Results are provided in Table 3, below.

TABLE 3 Sample 1 Sample 2 Tensile Modulus (MPa) 1994.00 1725.00 TensileBreak Stress (MPa) 45.04 45.20 Tensile Break Strain (%) 58.01 73.76 Std.Dev. 6.60 4.78

As can be seen, Sample 2 exhibited better tensile elongation and lowermodulus before and after annealing. However, no improvement in impactstrength was seen, which is believed to be due to a chain scissionreaction between the disulfide and the polypropylene sulfide.

Example 2

Materials as described in Example 1 were melt mixed using a Coperionco-rotating, fully-intermeshing, twin-screw extruder with an overall L/Dof 40 and ten temperature control zones including one at the die. A highshear screw design was used to compound the additives into a resinmatrix. The polyarylene sulfide, impact modifier and lubricant were fedto the main feed throat in the first barrel by means of a gravimetricfeeder. The disulfide was fed using a gravimetric feeder at variouslocations in the extruder; at the main feed throat, at barrel 4 andbarrel 6. The crosslinking agent was fed at barrel 6. Materials werefurther mixed then extruded through a strand die. The strands werewater-quenched in a bath to solidify and granulated in a pelletizer.

Comparative Samples 3 and 4 were formed of the same composition andcompounded by use of a different screw design.

TABLE 4 Addition Point 3 4 5 6 7 8 9 10 Lubricant main feed 0.3 0.3 0.30.3 0.3 0.3 0.3 0.3 Crosslinking barrel 6 — — 0.5 1.0 1.0 0.5 0.5 0.5Agent Disulfide main feed — — — — — 0.30 — — Disulfide barrel 4 — — — —— — 0.3 — Disulfide barrel 6 — — — — — — — 0.3 Impact main feed 15.015.0 15.0 15.0 10.0 15.0 15.0 15.0 Modifier Polyarylene main feed 84.784.7 84.2 83.7 88.7 83.9 83.9 83.9 Sulfide Total 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0

Following formation, tensile bars were formed and tested for a varietyof physical characteristics. Results are provided in Table 5, below.

TABLE 5 Sample Sample Sample Sample Sample Sample Sample Sample 3 4 5 67 8 9 10 Melt Viscosity 2423 — 2659 2749 2067 2349 2310 2763 (poise)Density (g/cm³) — 1.28 — 1.25 — — — — Tensile 2076 2800 2177 2207 25511845 2185 2309 Modulus (MPa) Tensile Break 46.13 — 45.40 48.27 51.7146.47 47.16 47.65 Stress (MPa) Tensile Break 33.68 25 43.97 35.94 26.9047.51 40.85 63.85 Strain (%) Elongation at 5.17 5 5.59 7.49 4.5 11.786.94 7.00 Yield (%) Yield 51.07 52 50.76 51.62 59.63 51.07 52.56 51.88Stress (MPa) Notched Charpy 22.30 30 23.90 39.40 14.80 12.50 19.70 39.90Impact Strength at 23° C. (kJ/m²) Notched Charpy 7.8 7 — 10 — — — 10.8Impact Strength at −30° C. (kJ/m²) DTUL (° C.) — 100 — 102 — — — — MeltTemp. (° C.) 280 280 280 280 280 280 280 280 Water — 0.05 — 0.05 — — — —absorption (%) Hydrocarbon volume 16 uptake (%)

Samples were annealed at 230° C. for 2 hours and re-tested for physicalcharacteristics. Results are provided in Table 6, below.

TABLE 6 Sample Sample Sample Sample Sample Sample Sample Sample 3 4 5 67 8 9 10 Tensile 2383 — 2339 2279 2708 2326 2382 2491 Modulus (MPa)Tensile Break 52.70 — 53.96 53.11 61.10 56.74 54.81 55.25 Stress (MPa)Tensile Break 29.42 — 20.97 35.76 20.34 31.37 41.23 49.03 Strain (%)Std. Dev. 6.84 — 6.95 6.66 5.40 2.83 2.65 3.74

As can be seen, the highest tensile elongation and highest impactstrength were observed for Sample 10, which includes both thecrosslinking agent and the disulfide added at the same point downstreamduring processing.

FIG. 21 illustrates the relationship of notched Charpy impact strengthover temperature change for Sample 3 and for Sample 6. As can be seen,the polyarylene sulfide composition of Sample 6 exhibits excellentcharacteristics over the entire course of the temperature change, with ahigher rate of increase in impact strength with temperature change ascompared to the comparison material.

FIG. 22 includes scanning electron microscopy images of the polyarylenesulfide used in forming the sample 3 composition (FIG. 22A) and theSample 6 composition (FIG. 22B). As can be seen, there is no clearboundary between the polyarylene sulfide and the impact modifier in thecomposition of FIG. 22B.

Tensile bar test specimens of samples 3, 6, and 10 were immersed in 10wt. % sulfuric acid for 500 hours at either 40° C. or 80° C. Tensileproperties and impact properties were measured before and after the acidexposure. Results are summarized in Table 7 below.

TABLE 7 Sample 3 Sample 6 Sample 10 Initial properties Tensile Modulus(MPa) 2076 2207 2309 Tensile Break Stress (MPa) 46.13 48.27 47.65Tensile Break Strain (%) 33.68 35.94 63.85 Charpy notched impact 22.3039.40 39.90 strength at 23° C. (kJ/m²) Properties after 500 hoursexposure in sulfuric acid at 40° C. Tensile Modulus (MPa) 2368 2318 2327Tensile Break Stress (MPa) 48.83 48.48 48.53 Tensile Break Strain (%)10.99 28.28 30.05 Charpy notched impact 18.4 33.6 35.9 strength at 23°C. (kJ/m²) Loss in Charpy notched impact 18 15 15 strength (%)Properties after 500 hour exposure in sulfuric acid at 80° C. TensileModulus (MPa) 2341 2356 2354 Tensile Break Stress (MPa) 49.61 48.0448.86 Tensile Break Strain (%) 10.60 19.88 26.32 Charpy notched impact9.2 31.0 34.0 strength at 23° C. (kJ/m²) Loss in Charpy notched impact59 21 15 strength (%)

The results in the change in Charpy notched impact strength over timeduring exposure to the acid solution at an elevated temperature areillustrated in FIG. 23. As can be seen, the relative loss of strength ofsamples 6 and 10 is much less than the comparison sample.

Example 3

Materials as described in Example 1 were melt mixed using a Coperionco-rotating, fully-intermeshing, twin-screw extruder with an overall L/Dof 40 and ten temperature control zones including one at the die. A highshear screw design was used to compound the additives into a resinmatrix. The polyarylene sulfide, impact modifier and lubricant were fedto the feed throat in the first barrel by means of a gravimetric feeder.The crosslinking agent was fed using a gravimetric feeder at the mainfeed throat and at barrel 6. Materials were further mixed then extrudedthrough a strand die. The strands were water-quenched in a bath tosolidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 8, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 8 Addition Sample Sample Sample Sample Component Point 11 12 13 14Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking main — 0.5 1.0 — Agentfeed Crosslinking barrel 6 — — — 1.0 Agent Impact main 15.0 15.0 15.015.0 Modifier feed Polyarylene main 84.7 84.2 83.7 83.7 Sulfide feedTotal 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested fora variety of physical characteristics. Results are provided in Table 9,below.

TABLE 9 Sample Sample Sample Sample 11 12 13 14 Melt Viscosity (poise)2649 2479 2258 3778 Tensile Modulus (MPa) 2387 2139 2150 1611 TensileBreak Stress 46.33 49.28 51.81 42.44 (MPa) Tensile Break Strain (%)24.62 22.60 14.45 53.62 Std. Dev. 9.19 1.51 2.23 1.90 Notched Charpy27.50 8.50 6.00 39.30 Impact Strength at 23° C. (kJ/m²) Std. Dev. 2.71.10 0.60 2.10

As can be seen, upstream feed of the crosslinking agent decreased theimpact properties of the composition, while downstream feed increasedthe tensile elongation by 118% and room temperature impact strength by43%.

Example 4

Materials as described in Example 1 were melt mixed using a Coperionco-rotating, fully-intermeshing, twin-screw extruder with an overall L/Dof 40 and ten temperature control zones including one at the die. A highshear screw design was used to compound the additives into a resinmatrix. The polyarylene sulfide, impact modifier and lubricant were fedto the feed throat in the first barrel by means of a gravimetric feeder.The crosslinking agent was fed using a gravimetric feeder at barrel 6.Materials were further mixed then extruded through a strand die. Thestrands were water-quenched in a bath to solidify and granulated in apelletizer.

Compositions of the samples are provided in Table 10, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 10 Addition Sample Sample Sample Sample Component Point 15 16 1718 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.7 1.01.7 Agent Impact main 25.0 25.0 15.0 15.0 Modifier feed Polyarylene main73.7 73.0 83.7 83.0 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested fora variety of physical characteristics. Results are provided in Table 11,below.

TABLE 11 Sample Sample Sample Sample 15 16 17 18 Melt Viscosity (poise)4255 4198 2522 2733 Density (g/cm³) 1.2 — — — Tensile Modulus (MPa)1582.00 1572.00 2183.00 2189.00 Tensile Break Stress 45.59 46.29 48.9849.26 (MPa) Tensile Break Strain 125.92 116.40 66.13 48.24 (%) Std. Dev.19.79 9.97 15.36 7.80 Elongation at Yield (%) 23 — — — Yield Stress(MPa) 42 — — — Flex Modulus (MPa) 1946.00 1935.00 2389.00 2408.00Flexural Stress @3.5% 48.30 48.54 68.55 68.12 (MPa) Notched Charpy 55.6051.80 43.60 19.10 Impact Strength at 23° C. (kJ/m²) Std. Dev. 1.00 1.401.50 1.50 Notched Charpy 13 — — — Impact Strength at −30° C. (kJ/m²)Notched Charpy 13.30 12.10 11.26 8.70 Impact Strength at −40° C. (kJ/m²)Std. Dev. 1.50 0.90 0.26 0.50 DTUL (1.8 MPa) (° C.) 97.20 97.60 101.70100.90 Water absorption (%) 0.07 — — —

Example 5

Materials as described in Example 1 were utilized except for thepolyarylene sulfide, which was Fortron® 0320 linear polyphenylenesulfide available from Ticona Engineering Polymers of Florence, Ky.Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide and impact modifier were fed to the feed throat inthe first barrel by means of a gravimetric feeder. The crosslinkingagent was fed using a gravimetric feeder at barrel 6. Materials werefurther mixed then extruded through a strand die. The strands werewater-quenched in a bath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 12, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 12 Addition Sample Sample Sample Sample Sample Component Point 1920 21 22 23 Crosslinking barrel 6 — — — 0.1 0.2 Agent Impact main feed —1.5 3.0 1.5 3.0 Modifier Polyarylene main feed 100.0 98.5 97.0 98.4 96.8Sulfide Total 100.0 100.0 100.0 100.0 100.0

Following formation, tensile bars formed of the samples were tested fora variety of physical characteristics. Results are provided in Table 13,below.

TABLE 13 Sample Sample Sample Sample Sample 19 20 21 22 23 MeltViscosity (poise) 2435 2684 2942 2287 1986 Tensile Modulus (MPa) 32083207 3104 3245 3179 Tensile Break Stress 67.20 72.94 59.06 63.95 60.80(MPa) Tensile Break Strain (%) 2.46 4.54 11.96 6.31 11.40 Std. Dev. 0.321.11 1.24 2.25 3.53 Flex Modulus (MPa) 3103.00 3173.00 3031.00 3284.003156.00 Flexural Stress @3.5% 105.76 104.74 100.21 109.09 104.81 (MPa)Notched Izod Impact 2.90 5.20 5.60 4.10 4.30 Strength at 23° C. (kJ/m²)Std. Dev. 0.40 0.40 0.40 0.20 0.20 DTUL (1.8 MPa) (° C.) 105.60 104.00103.70 104.20 104.80

Example 6

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfideavailable from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® 4720—a random terpolymer of ethylene, ethylacrylate and maleic anhydride available from Arkema, Inc.

Crosslinking Agent: Hydroquinone

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall LID of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at the main feed for samples 24 and 25and at barrel 6 for samples 26 and 27. Materials were further mixed thenextruded through a strand die. The strands were water-quenched in a bathto solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 14, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 14 Addition Sample Sample Sample Sample Sample Component Point 2425 26 27 28 Lubricant main feed 0.3 0.3 0.3 0.3 0.3 Crosslinking barrel6 — — — 0.1 0.2 Agent Crosslinking main feed — 0.1 0.2 — — Agent Impactmain feed 15.0 15.0 15.0 15.0 15.0 Modifier Polyarylene main feed 84.784.6 84.5 84.6 84.5 Sulfide Total 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 15, below.

TABLE 15 Sample Sample Sample Sample Sample 24 25 26 27 28 MeltViscosity 2435 2797 3251 2847 2918 (poise) Tensile Modulus 2222 21642163 2184 2145 (MPa) Tensile Break 52.03 45.17 46.53 45.47 46.39 Stress(MPa) Tensile Break 36.65 50.91 63.39 38.93 41.64 Strain (%) Std. Dev.9.09 14.9 11.88 7.62 10.42 Elongation at Yield (%) 5.75 5.49 5.76 5.535.70 Yield Stress (MPa) 52.03 50.21 50.77 51.39 50.85 Flexural Modulus2358.00 2287.00 2286.00 2305.00 2281.00 (MPa) Flexural Stress 70.5168.25 68.03 69.23 68.23 @3.5% (MPa) Notched Charpy 29.80 44.60 50.6042.30 45.90 Impact Strength at 23° C. (kJ/m²) Std. Dev. 4.10 2.40 1.901.90 1.60 Notched Charpy 5.90 9.30 11.00 9.60 9.80 Impact Strength at−40° C. (kJ/m²) Std. Dev. 1.00 0.90 1.20 0.80 1.30 DTUL (1.8 MPa) 99.1093.90 98.20 100.10 99.00 (° C.)

Example 7

Materials utilized to form the compositions included the following:

Polyarylene Sulfide:

PPS1—Fortron® 0203 linear polyphenylene sulfide available from TiconaEngineering Polymers of Florence, Ky.

PPS2—Fortron®0205 linear polyphenylene sulfide available from TiconaEngineering Polymers of Florence, Ky.

PPS3—Fortron®0320 linear polyphenylene sulfide available from TiconaEngineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene andglycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall L/D of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at barrel 6. Materials were further mixedthen extruded through a strand die. The strands were water-quenched in abath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 16, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 16 Addition Sample Sample Sample Sample Sample Sample ComponentPoint 29 30 31 32 33 34 Lubricant main feed 0.3 0.3 0.3 0.3 0.3 0.3Crosslinking barrel 6 1.0 1.0 1.0 Agent Impact main feed 15.0 15.0 15.015.0 15.0 15.0 Modifier PPS1 main feed 84.7 83.7 PPS2 main feed 84.783.7 PPS3 main feed 84.7 83.7 Total 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 17, below.

TABLE 17 Sample Sample Sample Sample Sample Sample 29 30 31 32 33 34Tensile 2292 2374 2250 2427 2130 2285 Modulus (MPa) Tensile Break 50.9250.18 49.18 53.22 48.01 48.08 Stress (MPa) Tensile Break 5.79 2.84 23.7934.73 23.55 45.42 Strain (%) Std. Dev. 0.99 0.18 11.96 4.01 18.57 18.94Flexural 2279.00 2382.00 2257.00 2328.00 2292.00 2294.00 Modulus (MPa)Flexural Stress 71.11 74.94 69.72 72.39 67.95 68.95 @3.5% (MPa) NotchedCharpy 5.70 3.70 9.10 12.80 19.40 45.40 Impact Strength at 23° C.(kJ/m²) Std. Dev. 0.90 0.70 0.80 1.00 2.70 7.70 Notched Charpy 3.00 2.505.10 5.00 5.10 8.00 Impact Strength at −40° C. (kJ/m²) Std. Dev. 0.700.30 0.60 0.30 0.40 1.00 DTUL (1.8 101.00 105.50 100.00 102.90 99.90100.40 MPa) (° C.)

Example 8

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfideavailable from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene andglycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall LID of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at barrel 6. Materials were further mixedthen extruded through a strand die. The strands were water-quenched in abath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 18, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 18 Addition Sample Sample Sample Sample Sample Sample ComponentPoint 35 36 37 38 39 40 Lubricant main feed 0.3 0.3 0.3 0.3 0.3 0.3Crosslinking barrel 6 0.75 1.25 1.75 Agent Impact main feed 15.0 15.025.0 25.0 35.0 35.0 Modifier Polyarylene main feed 84.7 83.95 74.7073.45 64.70 62.95 Sulfide Total 100.0 100.0 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 19, below. Sample 39 wasnot injection moldable.

TABLE 19 Sample Sample Sample Sample Sample Sample 35 36 37 38 39 40Melt Viscosity 2323 2452 2955 3821 2025 5462 (poise) Tensile 2281 22982051 1721 — 1045 Modulus (MPa) Tensile Break 47.09 49.09 47.29 46.18 —39.81 Stress (MPa) Tensile Break 28.92 36.42 97.33 110.36 — 96.76 Strain(%) Std. Dev. 6.35 3.13 53.94 8.40 — 1.77 Elongation at 5.28 8.58 36.00108.19 — 95.77 Yield (%) Yield 52.42 53.92 46.50 46.76 — 40.43 Stress(MPa) Flexural 2388.00 2349.00 2210.00 1750.00 — 1209.00 Modulus (MPa)Flexural Stress 71.52 71.70 63.15 50.52 — 34.41 @3.5% (MPa) NotchedCharpy 35.15 38.40 57.00 52.70 — 52.10 Impact Strength at 23° C. (kJ/m²)Std. Dev. 6.22 1.50 1.40 3.40 — 2.10 Notched Charpy 8.20 10.70 8.7018.10 — 14.10 Impact Strength at −30° C. (kJ/m²) Std. Dev. 1.50 1.600.20 0.90 — 0.80 Notched Charpy 7.26 9.20 8.00 16.80 — 12.47 ImpactStrength at −40° C. (kJ/m²) Std. Dev. 1.54 2.30 0.60 0.40 — 0.92 DTUL(1.8 99.90 103.60 98.10 99.30 — 92.70 MPa) (° C.) Water — — — — — 0.1absorption (%)

Example 9

Materials utilized to form the compositions included the following:

Polyarylene sulfide: Fortron® 0214 linear polyphenylene sulfideavailable from Ticona Engineering Polymers of Florence, Ky.

Impact Modifier: LOTADER® AX8840—a random copolymer of ethylene andglycidyl methacrylate available from Arkema, Inc.

Crosslinking Agent: Terephthalic Acid

Lubricant: Glycolube® P available from Lonza Group Ltd.

Materials were melt mixed using a Coperion co-rotating,fully-intermeshing, twin-screw extruder with an overall LID of 40 andten temperature control zones including one at the die. A high shearscrew design was used to compound the additives into a resin matrix. Thepolyarylene sulfide, impact modifier and lubricant were fed to the mainfeed throat in the first barrel by means of a gravimetric feeder. Uponmelting and mixing of the above ingredients, the crosslinking agent wasfed using a gravimetric feeder at barrel 6. Materials were further mixedthen extruded through a strand die. The strands were water-quenched in abath to solidify and granulated in a pelletizer.

Compositions of the samples are provided in Table 20, below. Amounts areprovided as weight percentages based upon the weight of the sample.

TABLE 20 Addition Sample Sample Sample Sample Component Point 41 42 4344 Lubricant main 0.3 0.3 0.3 0.3 feed Crosslinking barrel 6 1.0 1.11.25 1.25 Agent Impact main 15 20 25 30 Modifier feed Polyarylene main83.7 78.6 73.45 68.45 Sulfide feed Total 100.0 100.0 100.0 100.0

Following formation, samples were tested for a variety of physicalcharacteristics. Results are provided in Table 21, below.

TABLE 21 Sample Sample Sample Sample 41 42 43 44 Specific Gravity 1.251.20 1.15 1.20 (g/cm³) Tensile Modulus 2200 1600 1200 1700 (MPa) (50 mm/min) Tensile Break 50 42 40 46 Strength (MPa) (50 mm/min) Elongation at40 100 90 75 Break (%) (50 mm/min) Yield Stress (MPa) 55 42 40 48 (50mm/min) Yield Strain (%) 9 25 90 15 (50 mm/min) Flexural Modulus 22001700 1300 1900 (MPa) Flexural Strength 68 50 40 56 @3.5% (MPa) NotchedCharpy 40 55 50 50 Impact Strength at 23° C. (kJ/m²) Notched Charpy 1024 20 20 Impact Strength at −30° C. Unnotched Charpy Not Not Not NotImpact Strength at broken broken broken broken 23° C. DTUL (1.8 MPa) 102100 95 100 (° C.) Water absorption 0.05 0.07 0.1 0.05 (%) Vicatsoftening 270 270 270 270 temp. (A10N, ° C.) Vicat softening 200 160 110180 temp. (B50N, ° C.) Complex viscosity 79.994 289.27 455.19 — (0.1rad/sec, 310° C.) (kPa/sec) Hydrocarbon 14 23 19 volume uptake (%)

Samples 41, 42, and 43 were tested to determine complex viscosity aswell as melt strength and melt elongation as a function of Henckystrain. As a comparative material, Sample 3 as described in Example 2was utilized. Samples 41, 42 and 43 were done at 310° C. and sample 3was done at 290° C. Results are shown in FIG. 24, FIG. 25, and FIG. 26.

Example 10

Sample 42 described in Example 9 was utilized to form a blow molded 1.6gallon tank. The formed tank is illustrated in FIG. 27. Cross sectionalviews of the tank are presented in FIG. 28A and FIG. 28B. The formedtank has a good outer surface with regard to both visual inspection andfeel. As shown in FIG. 28A, an even wall thickness (about 3 mm) wasobtained and minimal sag was observed. As shown in FIG. 28B, thepinch-offs formed an excellent geometry.

Example 11

Samples 41, 42, and 43 described in Example 9 were tested to determinepermeation of various fuels including CE10 (10 wt. % ethanol, 45 wt. %toluene, 45 wt. % iso-octane), CM15A (15 wt. % methanol and 85 wt. %oxygenated fuel), and methanol. Sample No. 4 described in Example 2 wasutilized as a comparison material. Two samples of each material weretested.

Table 22, below provides the average sample thickness and effective areafor the samples tested with each fuel.

TABLE 22 Average Sample Sample Thickness (mm) Effective area (m²) CE10Aluminum blank - 1 1.50 0.00418 Aluminum blank - 2 1.50 0.00418 SampleNo. 4 - 1 1.47 0.00418 Sample No. 4 - 2 1.45 0.00418 Sample No. 41 - 11.47 0.00418 Sample No. 41 - 2 1.49 0.00418 Sample No. 42 - 1 1.470.00418 Sample No. 42 - 2 1.46 0.00418 Sample No. 43 - 1 1.45 0.00418Sample No. 43 - 2 1.47 0.00418 CM15A Aluminum blank - 1 1.50 0.00418Aluminum blank - 2 1.50 0.00418 Sample No. 4 - 1 1.48 0.00418 Sample No.4 - 2 1.49 0.00418 Sample No. 41 - 1 1.49 0.00418 Sample No. 41 - 2 1.500.00418 Sample No. 42 - 1 1.47 0.00418 Sample No. 42 - 2 1.48 0.00418Sample No. 43 - 1 1.46 0.00418 Sample No. 43 - 2 1.47 0.00418 MethanolAluminum blank - 1 1.50 0.00418 Aluminum blank - 2 1.50 0.00418 SampleNo. 4 - 1 1.49 0.00418 Sample No. 4 - 2 1.49 0.00418 Sample No. 41 - 11.49 0.00418 Sample No. 41 - 2 1.51 0.00418 Sample No. 42 - 1 1.480.00418 Sample No. 42 - 2 1.47 0.00418 Sample No. 43 - 1 1.47 0.00418Sample No. 43 - 2 1.48 0.00418

The daily weight losses for each material and each fuel are shown inFIGS. 29-31. Specifically, FIG. 29 shows the daily weight loss for thesamples during the permeation test of CE10, FIG. 30 shows the dailyweight loss for the samples during the permeation test of CM15A, andFIG. 31 shows the daily weight loss for the samples during thepermeation test of methanol.

The average permeation rates for each sample with each fuel are providedin Table 23. Note that Sample No. 43 takes a longer time to arrive atequilibrium, so the linear regression fitting was generated based ondata between days 42 and 65 for this material, while the linear regressfitting was generated for the other materials between days 32 and 65.For methanol, the linear regression fitting was generated based on databetween days 20 and 65, but with Sample No. 604, the methanol linearregression fitting was generated based on data between days 30 and 65.Some samples show negative permeability, which is because the weightloss of the sample was lower than that of the aluminum blank.

TABLE 23 Average Perme- Normalized Normalized ation - Average permeationpermeation 3 mm Permeation - (g-mm/ (g-mm/ thick- 3 mm Sample day-m²)day-m²) ness thickness CE10 Sample No. 4-1 0.06 0.05 ± 0.01 0.02 0.02 ±0   Sample No. 4-2 0.05 0.02 Sample No. 41-1 0.07 0.04 ± 0.04 0.02 0.01± 0.01 Sample No. 41-2 0.01 0.00 Sample No. 42-1 0.06 0.06 ± 0   0.020.02 ± 0   Sample No. 42-2 0.06 0.02 Sample No. 43-1 2020 2.51 ± 0.430.73 0.84 ± 0.14 Sample No. 43-2 2.81 0.94 CM15A Sample No. 4-1 0.490.18 ± 0.44 0.16 0.06 ± 0.15 Sample No. 4-2 −0.13 −0.04 Sample No. 41-10.50 0.11 ± 0.55 0.17 0.04 ± 0.18 Sample No. 41-2 −0.27 −0.09 Sample No.42-1 −0.13 0.27 ± 0.58 −0.04 0.09 ± 0.19 Sample No. 42-2 0.68 0.23Sample No. 43-1 2.04 2.29 ± 0.35 0.68 0.76 ± 0.12 Sample No. 43-2 2.530.84 Methanol Sample No. 4-1 0.37 0.25 ± 0.18 0.12 0.08 ± 0.06 SampleNo. 4-2 0.13 0.04 Sample No. 41-1 0.02 0.05 ± 0.05 0.01 0.02 ± 0.02Sample No. 41-2 0.08 0.03 Sample No. 42-1 0.28 0.25 ± 0.05 0.09 0.08 ±0.02 Sample No. 42-2 0.21 0.07 Sample No. 43-1 0.27 0.41 ± 0.2  0.090.14 ± 0.07 Sample No. 43-2 0.55 0.18 The error was derived from thestandard deviation of duplicates in each sample.

These and other modifications and variations to the present disclosuremay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present disclosure. Inaddition, it should be understood the aspects of the various embodimentsmay be interchanged, either in whole or in part. Furthermore, those ofordinary skill in the art will appreciate that the foregoing descriptionis by way of example only, and is not intended to limit the disclosure.

What is claimed is:
 1. A method for forming a polyarylene sulfidecomposition, the method comprising: feeding a polyarylene sulfide to amelt processing unit having a length, wherein the polyarylene sulfide isa linear polyarylene sulfide containing less than about 1 mol. % ofcross-linking units based on the total monomer units of the polyarylenesulfide; feeding an impact modifier to the melt processing unit, thepolyarylene sulfide and the impact modifier mixing in the meltprocessing unit along a blending length of the melt processing unit suchthat the impact modifier becomes distributed throughout the polyarylenesulfide, the impact modifier comprising a reactive epoxy functionality,the ratio of the length of the melt processing unit to the blendinglength of the melt processing unit being from about 5 to abut 40; andfeeding a polyfunctional crosslinking agent to the melt processing unitat the end of the blending length of the melt processing unit, thecrosslinking agent being fed to the melt processing unit followingdistribution of the impact modifier throughout the polyarylene sulfide,the crosslinking agent comprising reactive functionality that isreactive to the reactive epoxy functionality of the impact modifier; andallowing the crosslinking agent and the impact modifier to react withinthe melt processing unit to form a crosslinked epoxy-functionalizedimpact modifier; wherein the composition exhibits a tensile elongationat break of about 50% or more as determined in accordance with ISO Testno. 527 at a temperature of 23° C. and at a speed of 50 mm/min.
 2. Themethod according to claim 1, further comprising feeding a disulfidecompound to the melt processing unit, the disulfide compound comprisingreactive functionality at one or more terminal ends of the disulfidecompound.
 3. The method according to claim 2, wherein the reactivefunctionality of the disulfide compound is the same as the reactivefunctionality of the crosslinking agent.
 4. The method according toclaim 2, wherein the disulfide compound and the crosslinking agent areadded in conjunction with one another.
 5. The method according to claim1, further comprising forming the polyarylene sulfide compositionaccording to a formation method comprising one or more of extrusion,injection molding, blow-molding, thermoforming, foaming, compressionmolding, hot-stamping, fiber spinning, and pultrusion.
 6. The methodaccording to claim 1, further comprising extruding the polyarylenesulfide composition, wherein the extrusion process utilizes acompression ratio of between about 2.5:1 and about 4:1.
 7. The methodaccording to claim 6, wherein the extrusion process utilizes a barrelhaving a length and a diameter, the ratio of the barrel length to thebarrel diameter being from about 16 to about
 24. 8. The method accordingto claim 6, the extrusion process utilizing an extruder having at leastfour zones, the temperature of the first zone being from about 276° C.to about 288° C., the temperature of the second zone being from about282° C. to about 299° C., the temperature of the third zone being fromabout 282° C. to about 299° C., and the temperature of the fourth zonebeing from about 540° C. to about 580° C.
 9. The method according toclaim 6, the extrusion process utilizing a die, the temperature of thedie being from about 293° C. to about 310° C.
 10. The method accordingto claim 6, the extrusion process having a head pressure that is fromabout 690 kPa to about 6900 kPa.
 11. The method according to claim 1,wherein the epoxy-functionalized impact modifier is present in an amountof 20 wt. % to 40 wt. %.
 12. The method according to claim 1, whereinthe crosslinking agent is present in an amount of 0.75 wt. % to 1.75 wt.%.
 13. The method according to claim 1, wherein the polyarylene sulfideis present in an amount of 20 wt. % to about 90 wt. %.
 14. The methodaccording to claim 1, wherein the crosslinking agent includes adicarboxylic acid or salt thereof.
 15. The method according to claim 14,wherein the crosslinking agent includes terephthalic acid.
 16. Themethod according to claim 1, wherein the epoxy-functionalized impactmodifier includes methacrylic monomer units.
 17. The method according toclaim 16, the epoxy-functionalized impact modifier further includesα-olefin monomer units.
 18. The method according to claim 16, whereinthe epoxy-functionalized monomer units include epoxy-functionalizedmethacrylic monomer units.
 19. The method according to claim 11, whereinthe crosslinking agent is present in an amount of 1 wt. % to 2 wt. %.20. The method according to claim 19, wherein the composition exhibits atensile elongation at break of about 70% or more as determined inaccordance with ISO Test no. 527 at a temperature of 23° C. and at aspeed of 50 mm/min.
 21. The method according to claim 1, wherein theratio of the length of the melt processing unit to the blending lengthof the melt processing unit is from about 8 to about
 40. 22. The methodaccording to claim 1, wherein the ratio of the length of the meltprocessing unit to the blending length of the melt processing unit isfrom about 10 to about 40.